Color-developing agent, silver halide photographic light-sensitive material and image-forming method

ABSTRACT

There is disclosed a novel color-developing agent of a 1,2,4-thiadiazol-5-yl hydrazine type. There is also disclosed a silver halide photographic light-sensitive material which gives sufficient color formation by development and forms an image excellent in image quality and image storability, by using the color-developing agent. Further, there is disclosed an image-forming method using the light-sensitive material.

This application claims priority under 35 U.S.C. §§119 and/or 365 toJapanese Patent Application No's 11-90618, 11-90669 and 11-90734 filedin Japan on Mar. 31, 1999.

FIELD OF THE INVENTION

The present invention relates to a novel color-developing agent, asilver halide photographic light-sensitive material and image-formingmethod using the color-developing agent. Particularly, the presentinvention relates to a silver halide photographic light-sensitivematerial which is excellent in color-forming property in the developingstage and in storability of an image, and to an image-forming methodutilizing the light-sensitive material.

Furhter, the present invention relates to a color diffusion transfertype silver halide photographic light-sensitive material comprising anovel diffusible dye-forming color-developing agent and a coupler, andto an image-forming method using the light-sensitive material.Particularly, the present invention relates to a color diffusiontransfer type silver halide photographic light-sensitive materialexcellent in storability and sharpness of an image, and to animage-forming method using the light-sensitive material.

BACKGROUND OF THE INVENTION

In a color photographic light-sensitive material, when it is exposed andthereafter color-developed, the oxidized color-developing agent isreacted with a coupler to form an image.

The color-developing is attained, for instance, by dipping an exposedlight-sensitive material in an aqueous alkali solution (a developingsolution) in which a color-developing agent is dissolved. This techniquehave many problems, for example, a problem that the developing solutiontends to be deteriorated with the lapse of time and problems concerningtreatments of developing solution wastes.

As one effective measure to solve above problems, a method wherein anaromatic primary amine developing agent or its precursor is built in thehydrophilic colloid layer of a light-sensitive material is proposed.Further, a method wherein a sulfonylhydrazine-type developing agent isbuilt in the hydrophilic colloid layer of a light-sensitive material isproposed. Examples of these include methods described, for example, inU.S. Pat. No. 803 783, JP-B-58-14671 (“JP-B” means examined Japanesepatent publication), European Patent Nos. 545 491(A1) and 565 165(A1).

However, even these methods cannot attain satisfactory color formationwhen color-developed; and there is the problem of storage stability.

In the fields of silver halide photographic light-sensitive materials, aso-called color diffusion transfer method in which a diffusible dye isformed imagewise on a light-sensitive material and the image istransferred and fixed to an image-receiving material, to form a colorimage, is known technique, and many proposals concerned this have beenmade. Adopted in these methods is a method in which a diffusible dye isgenerally formed, as a function of developing of silver halide, from acompound (hereinafter called a colorant) produced by modifying apre-colored image-forming dye (pre-formed dye) to one which is resistantto diffusion. In the method like this, when the colorant is added to thesame layer as a silver halide emulsion, an unacceptable reduction insensitivity to exposure is caused by a filter effect of a dye portion.Hence, generally, in order not to face the problem, a method is adoptedin which an image-forming colorant is added to a layer more apart fromthe exposed surface with respect to the silver halide emulsion layer. Inthis method, although the above reduction in sensitivity which is causedby the filter effect is avoided, there is an inherent drawback thatdeveloping information is transferred from the silver halide emulsion tothe colorant inefficiently because the physical distance between thesilver halide emulsion and the colorant is large.

In order to improve these drawbacks, a so-called coupling system isproposed in U.S. Pat. No. 4,469,773 and JP-B-63-36487 in which system adye is formed by a coupling reaction between an oxidized product of adeveloping agent, which is produced as a function of the developing ofsilver halide, and a coupler. However, the color-developing agentdescribed therein has a difficulty in the compatibility of the storagestability and the activity of the coupling reaction and a difficulty inmodifying both the color-developing agent and the coupler to thosehaving resistance to diffusion.

Novel color-developing agents are proposed in JP-A-09-152702 (“JP-A”means unexamined published Japanese patent application) andJP-A-09-152705. In these methods, however, sufficient color-formingproperty is not obtained yet. Also, whether or not there are problemsconcerning the hue and color image stability of a dye to be formed, orthe color image stability of a dye to be formed is not mentioned inthose publications at all.

Particularly, the compounds described in the said JP-A-9-152705 have thedrawbacks that sharpness of a magenta dye to be formed is insufficientand the storage stability of a color image is also insufficient.

In JP-A-9-152702, there is a proposal concerning a heterocyclichydrazine developing agent having two or more nitrogen atoms. However,in this publication, there is no specific description concerningdiffusion transfer type silver halide photographic light-sensitivematerials and there is also nothing referring to specific properties(e.g., hue and stability) of a dye to be formed.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a novelcolor-developing agent. It is another object of the present invention toprovide a silver halide photographic light-sensitive material whichgives sufficient color formation by development and forms an imageexcellent in image quality and image storability, by using thecolor-developing agent. Still another object of the present invention isto provide an image-forming method using the light-sensitive material.

Further another object of the present invention is to provide a methodfor forming a diffusible magenta dye from a colorless color-developingagent and a colorless coupler, in which the magenta dye to be formed inthis method is excellent in sharpness and storage stability. Stillanother object of the present invention is to provide a color diffusiontransfer type silver halide photographic light-sensitive material whichmakes it possible to obtain sufficient color formation upon developmentand to form a color transfer image of excellent image quality. Anotherobject of the present invention is to provide an image-forming methodusing the light-sensitive material.

Other and further objects, features, and advantages of the inventionwill appear more fully from the following description.

DETAILED DESCRIPTION OF THE INVENTION

The present inventors found that the above objects of the presentinvention can be attained by the following means. (1) A color-developingagent represented by the following formula (1):

wherein X represents a substituent that has, as a substituent on thesubstituent, at least one substituent represented by —COOH, —NHSO₂R,—SO₂NHR, —SO₂NHCOR, —CONHSO₂R, —OH or —SH, in which R represents analkyl group, an aryl group or an aromatic heterocyclic group, each ofwhich may be substituted, and Z represents a carbamoyl group, an acylgroup, an alkoxycarbonyl group or an aryloxycarbonyl group.

(2) The color-developing agent according to the above (1), wherein Z inthe formula (1) is a carbamoyl group, which is a carbamoyl group havingone or more hydrogen atoms bonded on the nitrogen atom of the carbamoylgroup.

(3) A silver halide photographic light-sensitive material containing atleast one color-developing agent represented by formula (1) stated inthe above (1), in at least one hydrophilic colloid layer provided on asupport.

(4) An image forming method, comprising subjecting the silver halidephotographic light-sensitive material according to the above (3), toimagewise exposure, and subjecting the resultant light-sensitivematerial to development.

(5) The image forming method as stated in the above (4), wherein thedevelopment step comprises subjecting the silver halide photographiclight-sensitive material to heat development.

(6) The image forming method as stated in the above (4), wherein thedevelopment step comprises subjecting the silver halide photographiclight-sensitive material to development, in the presence of an alkaligenerated from a metal salt which is sparingly soluble in water and acomplexing agent of the metal salt.

(7) The image forming method as stated in the above (4), wherein thedevelopment step comprises subjecting the color diffusion transfer typesilver halide photographic light-sensitive material to development withan alkali processing solution.

(8) A color-developing agent represented by the following formula (2):

wherein X¹ represents a halogen atom, an alkylthio group, analkylsulfinyl group, an alkylsulfonyl group, an arylthio group, anarylsulfinyl group, an arylsulfonyl group or a sulfamoyl group, providedthat a further substituent which can be substituted on X¹ excludes ahydroxy group, a carboxyl group, a mercapto group, an aminosulfonylgroup, a carbonylaminosulfonyl group, a sulfonylamino group and asulfonylaminocarbonyl group, Z¹ represents a carbamoyl group, an acylgroup, an alkoxycarbonyl group or an aryloxycarbonyl group.

(9) The color-developing agent according to the above (8), wherein Z¹ inthe formula (2) is a carbamoyl group, which is a carbamoyl group havingone or more hydrogen atoms bonded on the nitrogen atom of the carbamoylgroup.

(10) A silver halide photographic light-sensitive material containing atleast one color-developing agent represented by formula (2) stated inthe above (8), in at least one hydrophilic colloid layer provided on asupport.

(11) An image forming method, comprising subjecting the silver halidephotographic light-sensitive material according to the above (10), toimagewise exposure, and subjecting the resultant light-sensitivematerial to development.

(12) The image forming method as stated in the above (11), wherein thedevelopment step comprises subjecting the silver halide photographiclight-sensitive material to heat development.

(13) The image forming method as stated in the above (11), wherein thedevelopment step comprises subjecting the silver halide photographiclight-sensitive material to development, in the presence of an alkaligenerated from a metal salt which is sparingly soluble in water and acomplexing agent of the metal salt.

(14) The image forming method as stated in the above (11), wherein thedevelopment step comprises subjecting the color diffusion transfer typesilver halide photographic light-sensitive material to development withan alkali processing solution.

(15) A color diffusion transfer type silver halide photographiclight-sensitive material comprising at least one color-developing agentrepresented by the following formula (3) and at least one couplerrepresented by the following formula (4), in at least one hydrophiliccolloid layer provided on a support:

wherein X² represents an alkyl group or an aryl group, and Z² representsa carbamoyl group, an acyl group, an alkoxycarbonyl group or anaryloxycarbonyl group:

 wherein R¹ represents a substituent, m is an integer from 0 to 4, inwhich when m is 2 or more, R¹s may be the same or different and may forma five- to seven-membered ring between them, Y¹ represents an arylgroup, an unsaturated heterocyclic group, an acyl group, analkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group or asulfonyl group, in which the groups each have an alkyl group and the sumof carbon atoms thereof are 6 or more in total.

(16) The color diffusion transfer type silver halide photographiclight-sensitive material according to the above (15), wherein Z² in theformula (3) is a carbamoyl group, which is a carbamoyl group having oneor more hydrogen atoms bonded on the nitrogen atom of the carbamoylgroup.

(17) The color diffusion transfer type silver halide photographiclight-sensitive material according to the above (15), wherein Y¹ in theformula (4) is an alkoxycarbonyl group or a carbamoyl group, in whichthe groups each have an alkyl group and the sum of carbon atoms thereofare 6 or more in total.

(18) An image forming method, comprising subjecting the color diffusiontransfer type silver halide photographic light-sensitive materialaccording to the above (15), (16) or (17), to imagewise exposure, andsubjecting the resultant light-sensitive material to development.

(19) The image forming method as stated in the above (18), wherein thedevelopment step comprises subjecting the color diffusion transfer typesilver halide photographic light-sensitive material to heat development.

(20) The image forming method as stated in the above (18), wherein thedevelopment step comprises subjecting the color diffusion transfer typesilver halide photographic light-sensitive material to development, inthe presence of an alkali generated from a metal salt which is sparinglysoluble in water and a complexing agent of the metal salt.

(21) The image forming method as stated in the above (18), wherein thedevelopment step comprises subjecting the color diffusion transfer typesilver halide photographic light-sensitive material to development withan alkali processing solution.

Herein, the color-developing agents as stated in the above (1) and (2),the silver halide photographic light-sensitive material as stated in theabove (3), and the image-forming methods as stated in the above (4) to(7) are referred to as the first embodiment of the present invention.

Further, the color-developing agents as stated in the above (8) and (9),the silver halide photographic light-sensitive material as stated in theabove (10), and the image-forming methods as stated in the above (11) to(14) are referred to as the second embodiment of the present invention.

In addition, the color diffusion transfer type silver halidephotographic light-sensitive materials as stated in the above (15) to(17), and the image-forming methods as stated in the above (18) to (21)are referred to as the third embodiment of the present invention.

In the following description, the present invention means to include allof the above first, second, and third embodiments, unless otherwisespecified.

Herein, in the present specification and claims, a group on a compoundincludes both a group having a substituent thereon and a group having nosubstituent (i.e. an unsubstituted group), unless otherwise specified.

The compound represented by the formula (1), which is used in the firstembodiment of the present invention will be explained in detail below.

Examples of the substituent represented by X in the formula (1) includean alkyl group (e.g., a methyl group, ethyl group and benzyl group), anaryl group (e.g., a phenyl group, naphthyl group and m-nitrophenylgroup), an alkylthio group (e.g., a methylthio group, ethylthio groupand benzylthio group), an alkylsulfinyl group (e.g., a methanesulfinylgroup and ethanesulfinyl group), an alkylsulfonyl group (e.g., amethanesulfonyl group, ethanesulfonyl group and benzylsulfonyl group),an arylthio group (e.g., a phenylthio group, naphthylthio group and4-methoxyphenylthio group), an arylsulfinyl group (e.g., benzenesulfinylgroup and naphthalenesulfinyl group), an arylsulfonyl group (e.g.,benzenesulfonyl groups, p-toluenesulfonyl group andp-methanesulfonylbenzenesulfonyl group) and a sulfamoyl group (e.g., anN-butylsulfamoyl group and N,N-diethylsulfamoyl group). Preferably eachof these groups has 1 to 50 carbon atoms and more preferably 1 to 20carbon atoms. Further these groups respectively have at least onesubstituent represented by —COOH, —NHSO₂R, —SO₂NHR, —SO₂NHCOR,—CONHSO₂R, —OH or —SH, in which R represents an alkyl group, an arylgroup or an aromatic heterocyclic group.

Among these groups, the substituent represented by X is preferably analkyl group, aryl group, alkylthio group, alkylsulfonyl group, arylthiogroup or arylsulfonyl group.

The substituent that X has is preferably —NHSO₂R, —SO₂NHR, —SO₂NHCOR,—CONHSO₂R or —OH, and more preferably —NHSO₂R or —SO₂NHR, in which Rrepresents an alkyl group (e.g., a methyl group, ethyl group or benzylgroup), an aryl group (e.g., a phenyl group, naphthyl group orm-nitrophenyl group) or an aromatic heterocyclic group (e.g., a2-pyridyl group, 4-pyridyl group or 2-furyl group), and preferably analkyl group or aryl group.

Z represents a carbamoyl group, acyl group, alkoxycarbonyl group oraryloxycarbonyl group. Among these groups, a carbamoyl group ispreferable and a carbamoyl group having one or two hydrogen atom(s), andmore preferably one hydrogen atom bonded on the nitrogen atom isparticularly preferable.

As the carbamoyl group, those having 1-50 carbon atoms are preferableand those having 8-40 carbon atoms are more preferable. Specificexamples of the carbamoyl group include a hexadecylcarbamoyl group,octadecylcarbamoyl group, 3-(2,4-di-tert-pentylphenoxy)propylcarbamoylgroup, 4-dodecyloxyphenylcarbamoyl group,2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group and naphthylcarbamoylgroup.

The aforementioned groups each may further have a substituent, andexamples of the further substituent include a cyano group, a carboxylgroup, a sulfo group, a hydroxy group, a nitro group, a mercapto group,a halogen atom (a fluorine atom, chlorine atom, bromine atom and iodineatom), an alkyl group (an alkyl group which has generally 30 or lesscarbon atoms and preferably 8 or less carbon atoms and may besubstituted, for example, a methyl group, trifluoromethyl group, benzylgroup, dimethylaminomethyl group, ethoxycarbonylmethyl group,acetylaminomethyl group, ethyl group, carboxyethyl group, allyl group,n-propyl group, iso-propyl group, n-butyl group, t-butyl group, t-pentylgroup, cyclopentyl group, n-hexyl group, t-hexyl group, cyclohexylgroup, t-octyl group, n-decyl group, n-undecyl group and n-dodecylgroup), an aryl group (an aryl group which has generally 30 or lesscarbon atoms and preferably 10 or less carbon atoms and may besubstituted, for example, a phenyl group, naphthyl group,3-hydroxyphenyl group, 3-chlorophenyl group, 4-acetylaminophenyl group,2-methanesulfonylphenyl group, 4-methoxyphenyl group,4-methanesulfonylphenyl group and 2,4-dimethylphenyl group), aheterocyclic group (a heterocyclic group which has generally 30 or lesscarbon atoms and preferably 10 or less carbon atoms and may besubstituted, for example, a 1-imidazolyl group, 2-furyl group, 2-pyridylgroup, 3-pyridyl group, 3,5-dicyano-2-pyridyl group, 5-tetrazolyl group,5-phenyl-1-tetrazolyl group, 2-benzthiazolyl group, 2-benzimidazolylgroup, 2-benzoxazolyl group, 2-oxazoline-2-yl group and morpholinogroup), an acyl group (an acyl group which has generally 20 or lesscarbon atoms and preferably 8 or less carbon atoms and may besubstituted, for example, an acetyl group, propionyl group, butyroylgroup, iso-butyroyl group, 2,2-dimethylpropionyl group, benzoyl group,3,4-dichlorobenzoyl group, 3-acetylamino-4-methoxybenzoyl group and4-methylbenzoyl group), a sulfonyl group (a sulfonyl group which hasgenerally 20 or less carbon atoms and preferably 8 or less carbon atomsand may be substituted, for example, a methanesulfonyl group,ethanesulfonyl group, chloromethanesulfonyl group, propanesulfonylgroup, butanesulfonyl group, n-octanesulfonyl group, n-dodecanesulfonylgroup, benzenesulfonyl group and 4-methylphenylsulfonyl group), analkoxy group (an alkoxy group which has generally 20 or less carbonatoms and preferably 8 or less carbon atoms and may be substituted, forexample, a methoxy group, ethoxy group, n-propyloxy group, iso-propyloxygroup and cyclohexylmethoxy group), an aryloxy group or heteroaryloxygroup (an aryloxy group or heteroaryloxy group which has generally 20 orless carbon atoms and preferably 10 or less carbon atoms and may besubstituted, for example, a phenoxy group, naphthyloxy group,4-acetylaminophenoxy group, pyrimidine-2-yloxy group and 2-pyridyloxygroup), a silyloxy group (a silyloxy group which has generally 10 orless carbon atoms and preferably 8 or less carbon atoms and may besubstituted, for example, a trimethylsilyloxy group andtert-butyldimethylsilyloxy group), an alkylthio group (an alkylthiogroup which has generally 20 or less carbon atoms and preferably 8 orless carbon atoms and may be substituted, for example, a methylthiogroup, ethylthio group, n-butylthio group, n-octylthio group,t-octylthio group, ethoxycarbonylmethylthio group, benzylthio group and2-hydroxyethylthio group), an arylthio group or heteroarylthio group (anarylthio or heteroarylthio group which has generally 20 or less carbonatoms and preferably 10 or less carbon atoms and may be substituted, forexample, a phenylthio group, 4-chlorophenylthio group,2-n-butoxy-5-t-octylphenylthio group, 4-nitrophenylthio group,2-nitrophenylthio group, 4-acetylaminophenylthio group,1-phenyl-5-tetrazolylthio group, 5-methanesulfonylbenzothiazole-2-ylgroup), a carbamoyl group (a carbamoyl group which has generally 20 orless carbon atoms and preferably 8 or less carbon atoms and may besubstituted, for example, a carbamoyl group, methylcarbamoyl group,dimethylcarbamoyl group, bis-(2-methoxyethyl)carbamoyl group,diethylcarbamoyl group, cyclohexylcarbamoyl group anddi-n-octylcarbamoyl group), a sulfamoyl group (a sulfamoyl group whichhas generally 20 or less carbon atoms and preferably 8 or less carbonatoms and may be substituted, for example, a sulfamoyl group,methylsulfamoyl group, dimethylsulfamoyl group,bis-(2-methoxyethyl)sulfamoyl group, diethylsulfamoyl group,di-n-butylsulfamoyl group, methyl-n-octylsulfamoyl group,3-ethoxypropylmethylsulfamoyl group and N-phenyl-N-methylsulfamoylgroup), an acylamino group (an acylamino group which has generally 20 orless carbon atoms and preferably 8 or less carbon atoms and may besubstituted, for example, an acetylamino group, 2-carboxybenzoylaminogroup, 3-nitrobenzoylamino group, 3-diethylaminopropanoylamino group andacryloylamino group), a sulfonylamino group (a sulfonylamino group whichhas generally 20 or less carbon atoms and preferably 8 or less carbonatoms and may be substituted, for example, a methanesulfonylamino group,benzenesulfonylamino group and 2-methoxy-5-n-methylbenzenesulfonylaminogroup), an alkoxycarbonylamino group (an alkoxycarbonylamino group whichhas generally 20 or less carbon atoms and preferably 8 or less carbonatoms and may be substituted, for example, a methoxycarbonylamino group,ethoxycarbonylamino group, 2-methoxyethoxycarbonylamino group,iso-butoxycarbonylamino group, benzyloxycarbonylamino group,t-butoxycarbonylamino group and 2-cyanoethoxycarbonylamino group), analkoxycarbonyloxy group (an alkoxycarbonyloxy group which has generally20 or less carbon atoms and preferably 8 or less carbon atoms and may besubstituted, for example, a methoxycarbonyloxy group, ethoxycarbonyloxygroup and methoxyethoxycarbonyloxy group), an aryloxycarbonylamino group(an aryloxycarbonylamino group which has generally 20 or less carbonatoms and preferably 8 or less carbon atoms and may be substituted, forexample, a phenoxycarbonylamino group, 2,4-nitrophenoxycarbonylaminogroup and 4-t-butoxyphenoxycarbonylamino group), an aminocarbonylaminogroup (an aminocarbonylamino group which has generally 20 or less carbonatoms and preferably 8 or less carbon atoms and may be substituted, forexample, a methylaminocarbonylamino group, morpholinocarbonylaminogroup, diethylaminocarbonylamino group,N-ethyl-N-phenylaminocarbonylamino group,4-cyanophenylaminocarbonylamino group and4-methanesulfonylaminocarbonylamino group), an aminocarbonyloxy group(an aminocarbonyloxy group which has generally 20 or less carbon atomsand preferably 8 or less carbon atoms and may be substituted, forexample, a dimethylaminocarbonyloxy group and pyrrolidinocarbonyloxygroup),an aminosulfonylamino group (an aminosulfonylamino group whichhas generally 20 or less carbon atoms and preferably 8 or less carbonatoms and may be substituted, for example, a diethylaminosulfonylaminogroup, di-n-butylaminosulfonylamino group and phenylaminosulfonylaminogroup), an amino group (an amino group which has generally 30 or lesscarbon atoms and preferably 8 or less carbon atoms and may besubstituted, for example, an amino group, methylamino group,dimethylamino group, ethylamino group, ethyl-3-carboxypropylamino group,ethyl-2-sulfoethylamino group, phenylamino group, methylphenylaminogroup and methyloctylamino group), an alkoxycarbonyl group (analkoxycarbonyl group which has generally 20 or less carbon atoms andpreferably 6 or less carbon atoms and may be substituted, for example, amethoxycarbonyl group, ethoxycarbonyl group and methoxyethoxycarbonylgroup), an aryloxycarbonyl group (an aryloxycarbonyl group which hasgenerally 20 or less carbon atoms and preferably 10 or less carbon atomsand may be substituted, for example, a phenoxycarbonyl group andp-methoxyphenoxycarbonyl group), an acyloxy group (an acyloxy groupwhich has generally 20 or less carbon atoms and preferably 8 or lesscarbon atoms and may be substituted, for example, an acetoxy group,benzoyloxy group, 2-butenoyloxy group and 2-methylpropanoyloxy group),an aryloxycarbonyloxy group (an aryloxycarbonyloxy group which hasgenerally 20 or less carbon atoms and preferably 8 or less carbon atomsand may be substituted, for example, a phenoxycarbonyloxy group,3-cyanophenoxycarbonyloxy group, 4-acetoxyphenoxycarbonyloxy group and4-t-butoxycarbonylaminophenoxycarbonyloxy group), and a sulfonyloxygroup (a sulfonyloxy group which has generally 20 or less carbon atomsand preferably 8 or less carbon atoms and may be substituted, forexample, a phenylsulfonyloxy group, methanesulfonyloxy group,chloromethanesulfonyloxy group, 4-chlorophenylsulfonyloxy group anddodecylsulfonyloxy group).

Next, examples of the color-developing agent represented by the formula(1) will be explained. However, the scope of the present invention isnot limited to these exemplified examples.

Next, the compound represented by the formula (2), which is used in thesecond embodiment of the present invention will be explained in detail.

X¹ in the formula (2) represents a halogen atom (e.g., a chlorine atomand bromine atom), an alkylthio group (e.g., a methylthio group,ethylthio group and cyanomethylthio group) which may have a substituent,an alkylsulfinyl group (e.g., a methanesulfinyl group and ethanesulfinylgroup) which may have a substituent, an alkylsulfonyl group (e.g., amethanesulfonyl group, ethanesulfonyl group and benzylsulfonyl group)which may have a substituent, an arylthio group (e.g., a phenylthiogroup, naphthylthio group and 4-methoxyphenylthio group) which may havea substituent, an arylsulfinyl group (e.g., a benzenesulfinyl group andnaphthalenesulfinyl group) which may have a substituent, an arylsulfonylgroup (e.g., a benzenesulfonyl group, p-toluenesulfonyl group andp-methanesulfonylbenzenesulfonyl group) which may have a substituent, ora sulfamoyl group (e.g., N,N-disubstituted sulfamoyl group, for example,an N,N-diethylsulfamoyl group) which may have a substituent. The numberof carbon atoms of each of these groups is preferably 1 to 50 and morepreferably 1 to 20.

Among these groups, a halogen atom, an alkylthio group, an alkylsulfonylgroup, an arylthio group and an arylsulfonyl group are preferable. Thesegroups may have a substituent.

Z¹ represents a carbamoyl group, an acyl group, an alkoxycarbonyl groupor an aryloxycarbonyl group. Among these groups, a carbamoyl group ispreferable, and a carbamoyl group having one or two and more preferablyone hydrogen atom bonded on the nitrogen atom is particularlypreferable.

As the carbamoyl group, those having 1-50 carbon atoms are preferableand those having 8-40 carbon atoms are more preferable. Specificexamples of the carbamoyl group include a hexadecylcarbamoyl group,octadecylcarbamoyl group, 3-(2,4-di-tert-pentylphenoxy)propylcarbamoylgroup, 4-dodecyloxyphenylcarbamoyl group,2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group and naphthylcarbamoylgroup.

As preferable examples of the aforementioned substituents, thosementioned as examples of the substituent that the group on the formula(1) may further have, can be mentioned. However, it is to be noted thata substituent that X¹ may have as a further substituent thereon, doesnot include a hydroxy group, carboxyl group, mercapto group,aminosulfonyl group, carbonylaminosulfonyl group, sulfonylamino group,and sulfonylaminocarbonyl group.

Next, examples of the color-developing agent represented by the formula(2) will be explained. However, the scope of the present invention isnot limited to these specific examples.

Next, the compounds represented by the formula (3) or (4) for use in thethird embodiment of the present invention will be explained in detail.

X² in the formula (3) represents preferably an alkyl group having 1 to 8carbon atoms which may have a substituent (e.g., a methyl group, ethylgroup, trifluoromethyl group, trichloromethyl group or cyanomethylgroup), or an aryl group having 6 to 15 carbon atoms which may have asubstituent (e.g., a phenyl group, naphthyl group or m-nitrophenylgroup).

Z² represents a carbamoyl group, acyl group, alkoxycarbonyl group oraryloxycarbonyl group. Among these groups, a carbamoyl group ispreferable and a carbamoyl group having one or two and preferably onehydrogen atom bonded on the nitrogen atom is particularly preferable.

As the carbamoyl group, those having 1-50 carbon atoms are preferableand those having 8-40 carbon atoms are more preferable. Specificexamples of the carbamoyl group include a hexadecylcarbamoyl group,octadecylcarbamoyl group, 3-(2,4-di-tert-pentylphenoxy)propylcarbamoylgroup, 4-dodecyloxyphenylcarbamoyl group,2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group and naphthylcarbamoylgroup.

In formula (4), R¹ represents a substituent. Examples of the substituentinclude a straight-chain or branched, chain or cyclic alkyl group having1 to 8 carbon atoms (e.g. trifluoromethyl, methyl, ethyl, propyl,heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl,cyclohexyl, octyl, and 2-ethylhexyl); a straight-chain or branched,chain or cyclic alkenyl group having 2 to 8 carbon atoms (e.g. vinyl,1-methylvinyl, and cyclohexen-1-yl); an alkynyl group having 2 to 8carbon atoms in all (e.g. ethynyl and 1-propinyl), an aryl group having6 to 15 carbon atoms (e.g. phenyl, and naphthyl), an acyloxy grouphaving 1 to 8 carbon atoms (e.g. acetoxy and benzoyloxy), a carbamoyloxygroup having 1 to 8 carbon atoms (e.g. N,N-dimethylcarbamoyloxy), acarbonamido group having 1 to 8 carbon atoms (e.g. formamido,N-methylacetamido, acetamido, N-methylformamido, and benzamido), asulfonamido group having 1 to 8 carbon atoms (e.g. methanesulfonamido,benzenesulfonamido, and p-toluenesulfonamido), a carbamoyl group having1 to 8 carbon atoms (e.g. N-methylcarbamoyl, N,N-diethylcarbamoyl, andN-mesylcarbamoyl), a sulfamoyl group having 0 to 8 carbon atoms (e.g.N-butylsulfamoyl, N,N-diethylsulfamoyl, andN-methyl-N-(4-methoxyphenyl)sulfamoyl), an alkoxy group having 1 to 8carbon atoms (e.g. methoxy, propoxy, isopropoxy, octyloxy, andt-octyloxy), an aryloxy group having 6 to 15 carbon atoms (e.g. phenoxy,4-methoxyphenoxy, and naphthoxy), an aryloxycarbonyl group having 7 to15 carbon atoms (e.g. phenoxycarbonyl and naphthoxycarbonyl), analkoxycarbonyl group having 2 to 10 carbon atoms (e.g. methoxycarbonyland t-butoxycarbonyl), an N-acylsulfamoyl group having 1 to 8 carbonatoms (e.g. N-propanoylsulfamoyl and N-benzoylsulfamoyl), analkylsulfonyl group having 1 to 8 carbon atoms (e.g. methanesulfonyl,octylsulfonyl, and 2-methoxyethylsulfonyl), an arylsulfonyl group having6 to 15 carbon atoms (e.g. benzenesulfonyl, and p-toluenesulfonyl), analkoxycarbonylamino group having 2 to 8 carbon atoms (e.g.ethoxycarbonylamino), an aryloxycarbonylamino group having 7 to 15carbon atoms (e.g. phenoxycarbonylamino and naphthoxycarbonylamino), anamino group having 0 to 8 carbon atoms (e.g. amino, methylamino,diethylamino, diisopropylamino, anilino, and morpholino), a cyano group,a nitro group, a carboxyl group, a hydroxyl group, a sulfo group, amercapto group, an alkylsulfinyl group having 1 to 8 carbon atoms (e.g.methanesulfinyl and octanesulfinyl), an arylsulfinyl having 6 to 15carbon atoms (e.g. benzenesulfinyl, 4-chlorophenylsulfinyl, andp-toluenesulfinyl), an alkylthio group having 1 to 8 carbon atoms (e.g.methylthio, octylthio, and cyclohexylthio), an arylthio group having 6to 15 carbon atoms (e.g. phenylthio and naphthylthio), a ureido grouphaving 1 to 15 carbon atoms (e.g. 3-methylureido, and3,3-dimethylureido), a heterocyclic group having 2 to 10 carbon atoms(e.g. a 3-membered to 12-membered monocyclic ring or condensed ringhaving at least one hetero atom(s), such as nitrogen, oxygen, andsulfur, for example, 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl,2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl,2-benzothiazolyl, and 2-benzoxazolyl), an acyl group having 1 to 8carbon atoms (e.g. acetyl, benzoyl, and trifluoroacetyl), asulfamoylamino group having 0 to 10 carbon atoms (e.g.N-butylsulfamoylamino and N-phenylsulfamoylamino), a silyl group having3 to 10 carbon atoms (e.g. trimethylsilyl, and dimethyl-t-butylsilyl),and a halogen atom (e.g. a fluorine atom, a chlorine atom, and a bromineatom).

The above substituents may further have a substituent, and examples ofsuch a substituent include those mentioned above as examples of R¹. Thetotal number of carbon atoms of the substituent is preferably 20 orless, more preferably 12 or less, and further preferably 8 or less.

m represents an inter of 0 to 4, and preferably 1 to 3.

When m is 2 or more, R¹s can be the same or different, and may bondtogether to form a 5- to 7-membered ring.

Y¹ represents an aryl group (e.g., a 4-hexadecyloxyphenyl group,4-dodecanoylaminophenyl group or2-chloro-4-hexadecyloxycarbonylaminophenyl group), an unsaturatedheterocyclic group (e.g., a 2-(5-dodecanoylamino)pyridyl group, an acylgroup (e.g., a dodecanoyl group or 4-decyloxybenzoyl group), analkoxycarbonyl group (e.g., a tetradecylcarbonyl group orhexadecylcarbonyl group), an aryloxycarbonyl group (e.g., a4-hexadecyloxyphenoxycarbonyl group or 4-dodecanoylaminophenoxycarbonylgroup), a carbamoyl group (e.g., an N,N-dicyclohexylcarbamoyl group orN-dodecylcarbamoyl group) or a sulfonyl group (e.g., a dodecylsulfonylgroup or hexadecylsulfonyl group), wherein these groups each have analkyl group whose sum of carbon atoms is 6 or more, preferably 6 to 50,and more preferably 12 to 40, in total. Also, these groups may have asubstituent. If the number of total carbon atoms of the alkyl groupbonded to Y¹ is 6 or more, this is effective to make the coupler of theformula (4) immobilized in a hydrophilic colloid layer and it makes easyto dissolve the coupler in a high-boiling point organic solvent, whichis hence preferable.

Examples of the substituent of X² in the formula (3) include the samesubstituents of R¹ in the formula (4) except for a sulfamoyl group,sulfonamide group, carboxyl group, hydroxyl group, mercapto group andsulfamoylamino group. Given as examples of the substituent of Z² in theformula (3) and of Y¹ in the formula (4) are the substituents having 1to 50 carbon atoms explained for R¹ in the formula (4).

Next, examples of the color-developing agent represented by the formula(3) will be explained. However, the scope of the present invention isnot limited to these specific examples.

Next, examples of the coupler represented by the formula (4) will beexplained. However, the scope of the present invention is not limited tothese specific examples.

Next, a general method of synthesizing the compound of the presentinvention will be explained.

SYNTHETIC EXAMPLE 1 Synthesis of Exemplified Compound (R-1)

A method of the synthesis of an exemplified compound (R-1) may refers tothe method described in JP-A-09-152702 and the compound (R-1) wassynthesized in the following synthetic process according toJP-A-09-152702. Other compounds may be synthesized in the similar manneras above.

Synthesis of Exemplified Compound (R-1)

Synthesis of Compound (T-3)

102.1 g of the compound (T-1) was suspended in 1 liter of methylenechloride, to which was added 100 g of perchloromethylmercaptan. Thereaction system was cooled to 0-5° C. and a solution in which 200 g ofsodium hydroxide was dissolved in 600 ml of water was added dropwise tothe reaction system such that the reaction temperature was kept at 15°C. or less. After the reaction was completed, the water phase wasremoved and 50 g of hydrazine hydrate was added dropwise to the organiclayer at 15° C. or less. After the reaction was completed, 1 liter ofwater was added to the reaction solution to carry out an extractionoperation. The organic layer was concentrated under reduced pressure toobtain an intermediate (T-3) in an amount of 137.5 g (58%).

Synthesis of Compound (T-5)

100.5 g of triphosgene was dissolved in 2 liter of tetrahydrofuran.Under cooling, 300.0 g of the compound (T-4) and then 150 ml oftriethylamine were added dropwise to the mixture. After the dropwiseaddition was completed, the reaction was continued 1 hour at roomtemperature, then 237.5 g of the compound (T-3) was divided into fiveparts which were separately added to the reaction mixture. After theaddition was completed, the reaction was further continued for 2 hours.To the reaction mixture were added 2 liters of ethyl acetate and 2liters of water to carry out extraction, followed by washing furtherwith 2 liter of water twice. Then, the organic layer was dried usingmagnesium sulfate anhydride and the solvent was distilled off underreduced pressure. The residue was recrystallized from acetonitrile toobtain 360.1 g (65%) of Compound (T-5) as white crystals.

Synthesis of Exemplified Compound (R-1)

27.7 g of the intermediate compound (T-5) was dissolved in 500 ml ofethyl acetate, 400 ml of water and 100 ml of ethanol, to which wasfurther added 87 g of sodium hydrosulfite. The mixture was reacted for 2hours and thereafter subjected to an extraction operation, followed bywashing with 500 ml of water twice. The organic layer was dried usingmagnesium sulfate anhydride and the solvent was distilled off underreduced pressure. The residue was dissolved in 100 ml of DMAC and 7 mlof triethylamine, to which was added dropwise 4.0 ml of methanesulfonylchloride under ice-cooling such that the internal temperature did notexceed 15° C. Then, the reaction was further run for 1 hour and thereaction mixture was poured into 500 ml of 1N hydrochloric acid. Theprecipitated crystals were collected by filtration and washed, followedby drying to obtain crude crystals. The crude crystals wererecrystallized from acetonitrile to obtain 24.1 g (80%) of Exemplifiedcompound (R-1) as white crystals.

SYNTHETIC EXAMPLE 2 Synthesis of Exemplified compound (R-101)

A method of the synthesis of an exemplified compound (R-101) may refersto the method described in JP-A-09-152702 and the compound (R-101) wassynthesized in the following synthetic process according toJP-A-09-152702.

Synthesis of Compound (T-6)

69.5 g of methylisothiourea was dissolved in 500 ml of methylenechloride, to which was then added 92.9 g of perchloromethylmercaptan. Asolution obtained by dissolving 100 g of sodium hydroxide in 200 ml ofwater was added dropwise to the mixture while controlling the internaltemperature at 50° C. or less under cooling using methanol/dry ice.After the dropwise addition was completed, the reaction was continued at15° C. or less for 1 hour and the reaction mixture was then subjected toan extraction operation. The extract was washed with 200 ml of watertwice. The organic layer was dried using magnesium sulfate anhydride andthe solvent was distilled off under reduced pressure. To the residue wasadded 200 ml of tetrahydrofuran and was then added dropwise 101 g ofhydrazine monohydrate under ice-cooling. In succession to the dropwiseaddition, the resulting mixture was reacted for one hour at roomtemperature, followed by addition of 200 ml of water to precipitatecrystals. The crystals were collected by filtration and washed with 300ml of acetonitrile, followed by drying. Thus, 58.3 g (72%) of a compound(T-6) was obtained as white crystals.

Synthesis of Exemplified Compound (R-101)

50.8 g of triphosgene was dissolved in 1 liter of tetrahydrofuran. 149.8g of the compound (T-4) and then 104 g of triethylamine were addeddropwise to the mixture while cooling. After the dropwise addition wascompleted, the reaction was continued for one hour at room temperature,then 64.8 g of the compound (T-6) was divided into five parts which wereseparately added to the reaction mixture. After the addition wascompleted, the reaction was further continued for 2 hours. To thereaction mixture were added 1 liter of ethyl acetate and 1 liter ofwater to carry out extraction, followed by washing further with 1 literof water twice. Then, the organic layer was dried using magnesiumsulfate anhydride and the solvent was distilled off under reducedpressure. The residue was recrystallized from acetonitrile to obtain118.9 g (62%) of Exemplified compound (R-101) as white crystals.

Synthesis of Exemplified Compounds (R-112) and (R-114)

Synthesis of Compound (T-7)

171.5 g of m-nitrobenzyl chloride and 80 g of thiourea were dissolved in1 liter of isopropyl alcohol and the mixture was heated under reflux for2 hours. In succession to the reaction, the reaction mixture was cooledto room temperature to collect the precipitated crystals by filtration,which were then washed with 300 ml of isopropyl alcohol. Thus, 237.6 g(96%) of a compound (T-7) was obtained as white crystals.

A compound (T-8) was synthesized according to the synthetic method ofthe Exemplified compound (R-101).

Synthesis of Compound (T-9)

57.5 g of the compound (T-8) was suspended in 300 ml of acetic acid, towhich was added dropwise 35 ml of aqueous 35% hydrogen peroxide solutionat an internal temperature of 50° C. The reaction system was completelyuniformed within one hour after the dropwise addition was finished andthus the reaction was completed. The reaction solution was poured into 1liter of 1N hydrochloric acid to collect the precipitated crystals byfiltration, which were then washed with water. The resulting crudecrystals were subjected to a silica gel column chromatography to obtain30.9 g (44%) of a compound (T-9) as white crystals from the eluate ofhexane/ethyl acetate (3:1).

A compound (T-10) and Exemplified compound (R-112) were synthesizedaccording to the synthetic method of Exemplified compound (R-101).

Synthesis of Exemplified Compound (R-114)

33.2 g of Exemplified compound (R-112) was dissolved in 500 ml of ethylacetate, 400 ml of water and 100 ml of ethanol, to which was furtheradded 87 g of sodium hydrosulfite. The mixture was reacted for 2 hoursand thereafter subjected to an extraction operation, followed by washingwith 500 ml of water twice. The organic layer was dried using magnesiumsulfate anhydride and the solvent was distilled off under reducedpressure. The residue was dissolved in 100 ml of DMAC and 7 ml oftriethylamine, to which was added dropwise 3.8 g of acetyl chlorideunder ice-cooling such that the internal temperature did not exceed 15°C. Then, the reaction was further run for 1 hour and the reactionmixture was poured into 500 ml of 1N hydrochloric acid. The precipitatedcrystals were collected by filtration and washed, followed by drying toobtain crude crystals. The crude crystals were recrystallized fromacetonitrile to obtain 25.3 g (68%) of Exemplified compound (R-114) aswhite crystals. Synthetic Example 3 Synthesis of Exemplified compound(R-201)

A method of the synthesis of Exemplified compound (R-201) is describedin detail in JP-A-09-152702 and the compound (R-201) was synthesized inthe following synthetic process according to JP-A-09-152702.

SYNTHETIC EXAMPLE 4 Synthesis of Exemplified Compound (MC-1)

The synthesis of the compound was carried out according to the followingsynthetic route.

Synthesis of Compound (T-11)

200 g of hydroquinone monobenzyl ether was dissolved in a mixturesolvent of 500 ml of acetonitrile and 500 ml of dimethylacetoamide(hereinafter abbreviated to as DMAC), to which 167 ml of triethylaminewas added. Then, 305 g of hexadecyl chloroformate was added dropwise tothe mixture in a room temperature atmosphere while the internaltemperature was controlled to be kept at 35° C. or less. After theaddition was completed, the reaction was continued for 1 hour andthereafter the reaction solution was poured into 3 liter of 1Nhydrochloric acid carefully. The precipitated crystals were collected byfiltration and washed with 300 ml of acetonitrile, followed by drying.Thus 435 g (93%) of a compound (T-11) was obtained as white crystals.

Synthesis of Compound (T-12)

47 g of the compound (T-11), 1 g of 10% Pd-C and 22 g of ammoniumformate were dissolved in 500 ml of methanol and the mixture was heatedunder reflux for 4 hours. After completion of the reaction, the catalystwas collected from the reaction solution by filtration using celite in aheated condition. 2 liter of water was poured into the filtrate and theprecipitated crystals were collected by filtration and washed with 100ml of methanol, followed by drying. Thus, a compound (T-12) was obtainedin an amount of 36.3 g (98%) as white crystals.

Synthesis of Compound (T-13)

37.8 g of the compound (T-12) was dissolved in 500 ml of methylenechloride, to which was added dropwise 8 ml of nitric acid with aspecific gravity of 1.38 in a room temperature atmosphere. The reactionwas further continued for 1 hour and 1 liter of hexane was poured intothe reaction solution and the precipitated crystals were collected byfiltration and washed with 100 ml of isopropyl alcohol, followed bydrying. Thus, a compound (T-13) was obtained in an amount of 34.7 g(82%) as yellow crystals.

Synthesis of Compound (T-14)

42.3 g of the compound (T-13) was dissolved in 200 ml of methanol, towhich was then added dropwise 85 ml of an aqueous sodium hypochloritesolution having an effective chlorine concentration of 5% in a roomtemperature atmosphere. The mixture was further reacted for 2 hours. 500ml of ethyl acetate and 800 ml of 1N hydrochloric acid were poured intothe reaction solution to perform an extraction operation, followed bywashing with 500 ml of water twice. Then, the organic layer was driedover magnesium sulfate anhydride and the solvent was distilled off underreduced pressure to obtain 35.2 g (77%) of a compound (T-14) as pale redcrystals. Synthesis of Exemplified Compound (MC-1)

45.7 g of the compound (T-14) was dissolved in 500 ml of ethyl acetate,400 ml of water and 100 ml of ethanol, to which was further added 87 gof sodium hydrosulfite. After the mixture was reacted for 2 hours, anextraction operation was performed, followed by washing with 500 ml ofwater twice. The organic layer was dried using magnesium sulfateanhydride and the solvent was distilled off under reduced pressure. Theresidue was dissolved in 100 ml of DMAC, to which was then addeddropwise 8 ml of acetyl chloride in a room temperature atmosphere whilethe internal temperature did not exceed 35° C. After the addition wascompleted, the resulting mixture was further reacted for 1 hour and thereaction mixture was poured into 500 ml of 1N hydrochloric acid. Theprecipitated crystals were collected by filtration, washed with waterand dried to obtain crude crystals. The crude crystals wererecrystallized from acetonitrile to obtain 31.9 g (68%) of Exemplifiedcompound (MC-1) as white crystals.

The color-developing agent of the present invention is used togetherwith a compound (a coupler) that can form a dye by oxidation couplingreaction. This coupler may be a so-called “four-equivalent coupler” or“two-equivalent coupler”, which is used in a conventional system using ap-phenylenediamine-series developing agent, but in the presentinvention, a “two-equivalent coupler” is preferable. Specific examplesof the coupler are described in detail, for example, in “Theory of ThePhotographic Process” (4th Ed., edited by T. H. James, Macmillan, 1977),pages 291 to 334 and 354 to 361, and in JP-A-58-12353, JP-A-58-149046,JP-A-58-149047, JP-A-59-11114, JP-A-59-124399, JP-A-59-174835,JP-A-59-231539, JP-A-59-231540, JP-A-60-2951, JP-A-60-14242,JP-A-60-23474, and JP-A-60-66249.

Examples of a coupler that is preferably used in the present inventioninclude couplers represented by formulae (1) to (12) described inJP-A-9-152705. Further, couplers (C-1) to (C-50) described inJP-A-9-152705, pages 24 to 37, and couplers (C-1) to (C-80) described inJP-A-8-286340, pages 29 to 44, can be mentioned as preferable examples,but the present invention is not limited to them.

Further, specific examples of a coupler that can be used in the presentinvention are shown below, but the present invention is not limited tothem.

Although the amount to be added, of the couplers that are used with thecolor developing agent of the present invention, varies according to themolar extinction coefficient (ε) of a produced dye, in order to obtainan image density of 1.0 or more in terms of reflection density, in thecase of couplers wherein the ε of the dye that will be produced bycoupling is of the order of 5,000 to 500,000, suitably the amount to beadded, of the couplers that are used in the present invention, is of theorder of generally 0.001 to 100 mmol/m², preferably 0.01 to 10 mmol/m²,and more preferably 0.05 to 5 mmol/m², in terms of the coated amount.

The amount of the color-developing agent of the present invention to beadded is generally 0.01 to 100 times, preferably 0.1 to 10 times, andmore preferably 0.2 to 5 times, the amount of the coupler in molarratio.

In the present invention, an auxiliary developing agent can bepreferably used. Herein the term “an auxiliary developing agent” means asubstance that functions to promote the transfer of electrons from thecolor-developing agent to silver halides in the development process ofthe silver halide development; and the auxiliary developing agent is acompound capable of releasing electrons according to the Kendall-Pelzrule.

As examples of these compounds, compounds (ETA-1) to (ETA-36) describedin JP-A-9-152705, and compounds D-1 to D-35 described in JP-A-9-146248can be mentioned.

In the present invention, a blocked photographic reagent that willrelease a photographically useful group at the time of processing can beused. As examples of these, those described in paragraphs 0073 to 0077of JP-A-9-152705 can be mentioned.

The light-sensitive material of the present invention, preferably, hason a base, a photosensitive silver halide, at least one color-developingagent represented by the above formula (1), (2), or (3), a coupler (whenthe compound represented by formula (3) is used as the color-developingagent, at least one coupler represented by the above formula (4)), and abinder, and, if required, an organic metal salt oxidant, and the likecan be contained. In many cases, these components are added to the samelayer, but they can be separately added to different layers if they arein reactive states.

Hydrophobic additives such as a color-developing agent, a coupler, andan image-formation-promoter explained later, which are used in thepresent invention may be introduced into the layers of thelight-sensitive material (i.e. photographic constitutional layers suchas hydrophilic colloid layer) by a known method such as a methoddescribed in U.S. Pat. No. 2,322,027. The color-developing agent and thecoupler can be preferably introduced into the same layer, although theymay be introduced into separate layers. When they are introduced intothe same layer, preferably they are introduced into the silver halideemulsion layer. Though an auxiliary developing agent may be added to anyone of the photographic constitutional layers, it is preferablyintroduced into a layer, such as the intermediate layer or theprotective layer, adjacent to the layers containing a silver halideemulsion. When these compounds are to be introduced into thephotographic structure layer, a high-boiling point organic solvent asdescribed in JP-A-59-83154, JP-A-59-178451, JP-A-59-178452,JP-A-59-178453, JP-A-59-178454, JP-A-59-178455 and JP-A-59-178457, U.S.Pat. Nos. 4,555,470, 4,536,466, 4,536,467, 4,587,206, 4,555,476,4,599,296, JP-B-3-62256 may be used, as required, together with alow-boiling point organic solvent having a boiling point as low as 50°C. to 160° C.

Further, these dye-donative compounds such as a coupler and acolor-developing agent, diffusion-proof reducing agents, high-boilingorganic solvents, and the like can be used singly, or in the form of acombination of two or more. As the case of color-developing agents, thecompound represented by formula (1), (2) or (3) can be used incombination with other compound that is not included in the formula.

The light-sensitive material of the third embodiment of the presentinvention may use couplers forming a yellow color, magenta color or cyancolor in combination with the compounds represented by the formulae (3)and (4). As these couplers, known couplers may be used in combination oftwo or more.

The amount of the high-boiling point organic solvent to be used isgenerally 10 g or less, preferably 5 g or less, and more preferably 1 gto 0.1 g, per g of a color-image forming compound to be used. The amountof the solvent is generally 1 cc or less, preferably 0.5 cc or less andmore preferably 0.3 cc or less based on 1 g of the binder.

For example, the amount of the high-boiling point organic solvent to beused is generally 10 g or less and preferably 5 g or less, per g of thetotal amount of the color-developing agent and the coupler to be used.

A dispersion method that use a polymer, as described in JP-B-51-39853and JP-A-51-59943, and a method wherein the addition is made with themin the form of a dispersion of fine particles, as described, forexample, in JP-A-6230242 and JP-A-63-271339, can also be used.

If the compounds are substantially insoluble in water, besides the abovemethods, a method can be used wherein the compounds may be made intofine particles to be dispersed and contained in a binder.

In dispersing the hydrophobic compound in a hydrophilic colloid, varioussurface-active agents can be used; examples are listed inJP-A-59-157636, pages (37) to (38), and in the RD publication shown in atable below.

In the photographic material of the present invention, use can be madeof a compound that can activate the development and make the imagestable. Preferable specific compounds for use are described in U.S. Pat.No. 4,500,626, the 51st column to the 52nd column.

In order to obtain colors ranging widely on the chromaticity diagram byusing three primary colors: yellow, magenta, and cyan, use is made of acombination of at least three silver halide emulsion layersphotosensitive to respectively different spectral regions. For examples,a combination of three layers of a blue-sensitive layer, agreen-sensitive layer, and a red-sensitive layer, and a combination of agreen-sensitive layer, a red-sensitive layer, and an infrared-sensitivelayer, can be mentioned. The photosensitive layers can be arranged invarious orders known generally for color photographic materials.Further, each of these photosensitive layers can be divided into two ormore layers if necessary.

In the photographic material, various auxiliary layers can be provided,such as a protective layer, an underlayer, an intermediate layer, anantihalation layer, and a backing layer. Further, in order to improvethe color separation, various filter dyes can be added.

The silver halide grains used in the present invention are made ofsilver bromide, silver chloride, silver chlorobromide, silverchloroiodide, silver iodobromide, or silver chloroiodobromide. Othersilver salts, such as silver rhodanate, silver sulfide, silver selenide,silver carbonate, silver phosphate, or a silver salt of an organic acid,may be contained in the form of independent grains or as part of silverhalide grains. If it is desired to make the development/desilvering(bleaching, fixing, and bleach-fix) step rapid, silver halide grainshaving a high silver chloride content are desirable. Further, if thedevelopment is to be restrained moderately, it is preferable to containsilver iodide. The preferable silver iodide content varies depending onthe intended photographic material. For example, in the case of X-rayphotographic materials, the preferable silver iodide content is in therange of 0.1 to 15 mol %, and in the case of graphic art and microphotographic materials, the preferable silver iodide content is in therange of 0.1 to 5 mol %. In the case of photographic materials forshooting represented by color negatives, preferably silver halidecontains 1 to 30 mol %, more preferably 5 to 20 mol %, and particularlypreferably 8 to 15 mol %, of silver iodide. It is preferable toincorporate silver chloride in silver iodobromide grains, because thelattice strain can be made less intense.

The grains of the silver halide emulsion for use in the presentinvention preferably have a distribution or a structure with respect tothe halogen composition. Typical examples thereof are grains having adouble structure, or core-shell-type grains wherein the halogencomposition is different in the surface layer and the inside part of thegrains, as disclosed, respectively, in JP-B-43-13162 and inJP-A-61-215540, JP-A-60-222845, and JP-A-61-75337. Instead of a simpledouble structure, a triple structure, as described in JP-A-60-222844, aneven larger-number multilayer structure, or a structure wherein thesurface of grains having a core-shell double structure has a thin silverhalide layer different in composition from that of the said surface, canbe used.

In order to make the inside of grains have a structure, not only theenclosing structure, as mentioned above, but also a so-call Functionedstructure can be used to form grains. Examples thereof are disclosed,for example, in JP-A-59-133540 and JP-A-58-108526, European Patent No.199 290(A2), JP-B-58-24772, and JP-A-59-16254. Crystals to be junctionedhave a composition different from that of host crystals, and they can bejunctioned and formed at the edges, corners, or planes of the hostcrystals. Such Functioned crystals can be formed if host crystals have auniform halogen composition or a core-shell-type structure.

In the case of a Functioned structure, not only a combination of silverhalides but also a combination of a silver halide with a silver saltcompound having no rock salt structure, such as silver rhodanate andsilver carbonate, can be used for the functioned structure. A non-silversalt compound, such as lead oxide, may be used if a junctioned structureis possible.

In the case of grains of silver iodobromide or the like having thesestructures, a preferable mode is that the core part is higher in silveriodide content than the shell part. Reversely, in some cases, grainshaving a lower silver iodide content in the core part than in the shellpart are preferable. Similarly, in the case of grains having ajunctioned structure, the silver iodide content of the host crystals isrelatively higher than that of the junctioned crystals, or this may bereversed. The boundary part of the grains having these structures inwhich different halogen compositions are present, may be distinct orindistinct. Also preferable is a mode wherein the composition iscontinuously changed positively.

It is important that in the case of that two or more silver halides arepresent as mixed crystals, or as silver halide grains having structures,the halogen composition distribution amoung grains is controlled. Themethod of measuring the halogen composition distribution among grains isdescribed in JP-A-60-254032. A desirable property is that the halogendistribution among grains is uniform. In particular, a highly uniformemulsion having a deviation coefficient of 20% or below is preferable.Another preferable mode is an emulsion in which the grain size and thehalogen composition are correlated. An example correlation is a largergrain size with a larger iodine content, and vice versa (smaller grainsize, lower iodine content). Depending on the purpose, the reversedcorrelation or a correlation using some other halogen composition can beused. For this purpose, it is preferable to mix two or more emulsionsdifferent in composition.

It is important to control the silver halide composition near thesurface of grains. An increase in the silver iodide content or thesilver chloride content at the part near the surface changes theadsorption of a dye or the developing speed. Therefore, the silverhalide composition can be chosen in accordance with the purpose. Tochange the halogen composition at the part near the surface, either thestructure enclosing the whole of a grain or the structure wherein onlypart of a grain is attached another silver halide different in halogencomposition, can be chosen. For example, in the case of atetradecahedral grain having (100) and (111) planes, only one plane ischanged in halogen composition, or in another case, one of the mainplane and the side plane of a tabular grain is changed in halogencomposition.

In the silver halide grains used in the present invention, in accordancewith the purpose, any of regular crystals having no twin plane, andthose described in “Shashin Kogyo no Kiso, Ginen Shashin-hen”, edited byNihon Shashin-gakkai (Corona Co.), page 163, such as single twins havingone twin plane, parallel multiple twins having two or more parallel twinplanes, and nonparallel multiple twins having two or more nonparalleltwin planes, can be chosen and used. An example in which grainsdifferent in shape are mixed is disclosed in U.S. Pat. No. 4,865,964,and if necessary this method can be chosen. In the case of regularcrystals, cubes having (100) planes, octahedrons having (111) planes,and dodecahedral grains having (110) planes, as disclosed inJP-B-55-42737 and JP-A-60-222842, can be used. Further, (h11) planegrains represented by (211), (hh1) plane grains represented by (331),(hk0) plane grains represented by (210) planes, and (hk1) plane grainsrepresented by (321) planes, as reported in “Journal of ImagingScience”, Vol. 30, page 247 (1986), can be chosen and used in accordancewith the purpose, although the preparation is required to be adjusted.Grains having two or more planes in one grain, such as tetradecahedralgrains having (100) and (111) planes in one grain, grains having (100)and (110) planes in one grain, or grains having (111) and (110) planesin one grain, can be chosen and used in accordance with the purpose.

The value obtained by dividing the diameter of the projected area, whichis assumed to be a circle, by the thickness of the grain, is called anaspect ratio, which defines the shape of tabular grains. Tabular grainshaving an aspect ratio of more than 1 can be used in the presentinvention. Tabular grains can be prepared by methods described, forexample, by Cleav in “Photography Theory and Practice” (1930), page 131;by Gutof in “Photographic Science and Engineering”, Vol. 14, pages 248to 257 (1970); and in U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,and 4,439,520, and British Patent No. 2 112 157. When tabular grains areused, such merits are obtained that the covering power is increased andthe color sensitization efficiency due to a sensitizing dye isincreased, as described in detail in the above-mentioned U.S. Pat. No.4,434,226. The average aspect ratio of 80% or more of all the projectedareas of grains is preferably 1 or more but less than 100, morepreferably 2 or more but less than 20, and particularly preferably 3 ormore but less than 10. As the shape of average grains, a triangle, ahexagon, a circle, and the like can be chosen. A regular hexagonal shapehaving six approximately equal sides, described in U.S. Pat. No.4,798,354, is a preferable mode.

In many cases, the grain size of tabular grains is expressed by thediameter of the projected area assumed to be a circle, and grains havingan average diameter of 0.6 microns or below, as described in U.S. Pat.No. 4,748,106, are preferable, because the quality of the image is madehigh. An emulsion having a narrow grain size distribution, as describedin U.S. Pat. No. 4,775,617, is also preferable. It is preferable torestrict the shape of tabular grains so that the thickness of the grainsmay be 0.5 microns or below, and more preferably 0.3 microns or below,because the sharpness is increased. Further, an emulsion in which thegrains are highly uniform in thickness, with the deviation coefficientof grain thickness being 30% or below, is also preferable. Grains inwhich the thickness of the grains and the plane distance between twinplanes are defined, as described in JP-A-63-163451, are also preferable.

In the case of tabular grains, the dislocation lines can be observed bya transmission electron microscope. In accordance with the purpose, itis preferable to choose grains having no dislocation lines, grainshaving several dislocation lines, or grains having many dislocationlines. Dislocation introduced straight in a special direction in thecrystal orientation of grains, or curved dislocation, can be chosen, andit is possible to choose from, for example, dislocation introducedthroughout grains, dislocation introduced in a particular part ofgrains, and dislocation introduced limitedly to the fringes of grains.In addition to the case of introduction of dislocation lines intotabular grains, also preferable is the case of introduction ofdislocation lines into regular crystalline grains or irregular grains,represented by potato grains. In this case, a preferable mode is thatintroduction is limited to a particular part of grains, such as vertexesand edges.

The silver halide emulsion used in the present invention may besubjected to a treatment for making grains round, as disclosed, forexample, in European Patent No. 96 412(B1), or it may be improved in thesurface, as disclosed in West Germany Patent No. 2 306 447(C2) andJP-A-60-221320.

Generally, the grain surface has a flat structure, but it is alsopreferable in some cases to make the grain surface uneven intentionally.Examples are a technique in which part of crystals, for example,vertexes and the centers of planes, are formed with holes, as describedin JP-A-58-106532 and JP-A-60-221320, and ruffled grains, as describedin U.S. Pat. No. 4,643,966.

The grain size of the emulsion used in the present invention isevaluated, for example, by the diameter of the projected area equivalentto a circle using an electron microscope; by the diameter of the grainvolume equivalent to a sphere, calculated from the projected area andthe grain thickness; or by the diameter of a volume equivalent to asphere, using the Coulter Counter method. A selection can be made fromultrafine grains having a sphere-equivalent diameter of 0.05 microns orbelow, and coarse grains having a sphere-equivalent diameter of 10microns or more. Preferably, grains of 0.1 microns or more but 3 micronsor below are used as photosensitive silver halide grains.

As the emulsion used in the present invention, an emulsion having a widegrain size distribution, that is, a so-called polydisperse emulsion, oran emulsion having a narrow grain size distribution, that is, aso-called monodisperse emulsion, can be chosen and used in accordancewith the purpose. As the scale for representing the size distribution,the diameter of the projected area of the grain equivalent to a circle,or the deviation coefficient of the sphere-equivalent diameters, isused. If a monodisperse emulsion is used, it is good to use an emulsionhaving such a size distribution that the deviation coefficient ispreferably 25% or below, more preferably 20% or below, and further morepreferably 15% or below.

In some cases, a monodisperse emulsion is defined by the average grainsize distribution based on the weight or number of grains. Further, inorder to allow the photographic material to satisfy the intendedgradation, in an emulsion layer having substantially the same colorsensitivity, two or more monodisperse silver halide emulsions differentin grain size are mixed and applied to the same layer or are applied asoverlaid layers. Further, two or more polydisperse silver halideemulsions can be used as a mixture; or they can be used to form overlaidlayers; or a combination of a monodisperse emulsion and a polydisperseemulsion can be used as a mixture; or the combination can be used toform overlaid layers.

As an emulsion used in the present invention, use can be made of anemulsion containing the above grains. One mode of carrying out thepresent invention is that the color-developing agent of the presentinvention and the emulsion comprising tabular grains whose silverchloride content is 50 mol % or more, are not used in combination.

As the photographic emulsion used in the present invention, any silverhalide emulsion prepared by a method described, for example, by P.Glafkides in “Chemie et Phisique Photographique,” Paul Montel, 1967; byG. F. Duffin in “Photographic Emulsion Chemistry,” Focal Press, 1966; orby V. L. Zelikman et al. in “Making and Coating Photographic Emulsion,”Focal Press, 1964, can be used. That is, any of the acid process, theneutral process, the ammonia process, and the like can be used; and toreact a soluble silver salt with a soluble halogen salt, any of thesingle-jet method, the double-jet method, a combination thereof, and thelike can be used. A method wherein grains are formed in the presence ofexcess silver ions (the so-called reverse precipitation process) canalso be used. As one type of the double-jet method, a method wherein pAgin the liquid phase, in which a silver halide will be formed, is keptconstant, that is, the so-called controlled double-jet method, can alsobe used. According to this method, a silver halide emulsion wherein thecrystals are regular in shape and whose grain size is approximatelyuniform, can be obtained.

A method in which previously precipitated silver halide grains are addedto a reaction vessel for the preparation of an emulsion, and the methodsdescribed, for example, in U.S. Pat. Nos. 4,334,012, 4,301,241, and4,150,994, are preferable in some cases. These can be used as seedcrystals, or they are effective when they are supplied as a silverhalide for growth. In the latter case, it is preferable to add anemulsion whose grains are small in size, and as an addition method, oneof the following can be chosen: all of the volume is added at onestroke, or the volume is separated and added in portions, or it is addedcontinuously. Further, in some cases, it is also effective to add grainshaving different halogen compositions in order to modify the surface.

The method in which a large part or only a small part of the halogencomposition of silver halide grains is converted by the halogenconversion method is disclosed, for example, in U.S. Pat. Nos. 3,477,852and 4,142,900, European Patent Nos. 273 429 and 273 430, and West GermanPublication Patent No. 3 819 241, and it is an effective method forforming grains. To convert to a more hardly soluble silver salt, it ispossible to add a solution of a soluble halogen or to add silver halidegrains. Selection can be made from respective methods in which theconversion is made at one stroke, in several steps, and continuously.

In addition to the method in which the grain growth is made by adding asoluble silver salt and a halogen salt at constant concentrations and atconstant flow rates, grain formation methods wherein the concentrationis changed or the flow rate is changed, as described in British PatentNo. 1 469 480 and U.S. Pat. Nos. 3,650,757 and 424,445, are preferablemethods. By changing the concentration or increasing the flow rate, theamount of the silver halide to be supplied can be changed as a linearfunction, a quadratic function, or a more complex function, of theaddition time. Further, if required, the amount of the silver halide tobe supplied is decreased, which is preferable in some cases. Alsoeffective is an addition method wherein, when several soluble silversalts different in solution composition are added, or when severalsoluble halogen salts different in solution composition are added, oneof them is increased and the other is decreased.

A mixing vessel that is used when a solution of a soluble silver saltand a solution of a soluble halogen salt are reacted can be selected foruse from methods described in U.S. Pat. Nos. 2,996,287, 3,342,605,3,415,650, and 3,785,777, and West German Publication Patent Nos. 2 556885 and 2 555 364.

For the purpose of promoting the ripening, a silver halide solvent isuseful. For example, it is known to allow an excess amount of halideions to be present in the reaction vessel, to promote the ripening.Further, other ripening agent can be used. All of the amount of theseripening agents may be blended in the dispersion medium in the reactionvessel before silver and halide salts are added, or their introductioninto the reaction vessel may be carried out together with the additionof a halide, a silver salt, or a peptitizer. As another modified mode, amethod is possible wherein a ripening agent is added independently atthe step of adding a halide salt and a silver salt.

For example, ammonia, thiocyanates (e.g. potassium rhodanate andammonium rhodanate), organic thioether compounds (e.g. compoundsdescribed, for example, in U.S. Pat. Nos. 3,574,628, 3,021,215,3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130, and 4,782,013,and JP-A-57-104926), thion compounds (e.g. tetra-substituted thioureasdescribed, for example, in JP-A-53-82408 and JP-A-55-77737, and U.S.Pat. No. 4,221,863; and compounds described in JP-A-53-144319), mercaptocompounds capable of promoting the growth of silver halide grains, asdescribed in JP-A-57-202531, and amine compounds (e.g. described inJP-A-54-100717), can be mentioned.

As a protective colloid and as a binder of other hydrophilic colloidlayers that are used when the emulsion according to the presentinvention is prepared, gelatin is used advantageously, but anotherhydrophilic colloid can also be used.

Use can be made of, for example, a gelatin derivative, a graft polymerof gelatin with another polymer, a protein, such as albumin and casein;a cellulose derivative, such as hydroxycellulose,carboxymethylcellulose, and cellulose sulfate; sodium alginate, a starchderivative, acacia, a saccharide derivative of a natural compound, suchas a polysaccharide, including dextran and pullulan; and many synthetichydrophilic polymers, including homopolymers and copolymers, such as apolyvinyl alcohol, a polyvinyl alcohol partial acetal, apoly-N-vinylpyrrolidone, a polyacrylic acid, a polymethacrylic acid, apolyacrylamide, a polyvinylimidazole, and a polyvinylpyrazole. Further,use can be made of a high-water-absorptive polymer described, forexample, in U.S. Pat. No. 4,960,681 and JP-A-62-245,260, that is, acopolymer of a vinyl monomer having —COOM or —SO₃M (wherein M representsa hydrogen atom or an alkali metal), or a copolymer of these vinylmonomers, or a copolymer of this vinyl monomer with another vinylmonomer (e.g. sodium methacrylate, ammonium methacrylate, and SumikagelL-5H [trade name; manufactured by Sumitomo Chemical Co., Ltd.]). Two ormore of these binders can be used in combination. A combination ofgelatin with these binders is also preferable.

As the gelatin, one of lime-processed gelatin, acid-processed gelatin,and so-called de-ashed gelatin wherein the content of calcium or thelike is reduced, can be selected, or a combination of them is alsopreferable. Enzyme-processed gelatin described in Bull. Soc. Sci. Photo.Japan, No. 16, page 30 (1966), may also be used, and a hydrolyzate orenzymolyzate of gelatin can also be used. For the preparation of tabulargrains, it is preferable to use a low-molecular-weight gelatin describedin JP-A-1-158426.

In the case of a heat-developable photographic material, an organicsilver salt oxidizing agent may be used together with a photosensitivesilver halide emulsion, and, as organic compounds capable of being usedto form it, there are benzotriazoles described in U.S. Pat. No.4,500,626, columns 52 to 53, aliphatic acids, and other compounds. Anacetylene silver described in U.S. Pat. No. 4,775,613 is also useful. Itis possible to use the organic silver salts in the form of a combinationof two or more.

These organic silver salts are used in an amount of generally 0.01 to 10mol, and preferably 0.01 to 1 mol, per mol of the photosensitive silverhalide. The total coating amount of the photosensitive silver halideemulsion and the organic silver salt is generally 0.05 to 10 g/m², andmore preferably 0.1 to 4 g/m², in terms of silver.

Preferably, the emulsion according to the present invention is washedwith water for desalting and is dispersed in a freshly preparedprotective colloid. The temperature at which the washing with water iscarried out can be selected in accordance with the purpose, andpreferably the temperature is selected in the range of 5 to 20° C. ThepH at which the washing is carried out can be selected in accordancewith the purpose, and preferably the pH is selected in the range of 2 to10, and more preferably in the range of 3 to 8. The pAg at which thewashing is carried out can be selected in accordance with the purpose,and preferably the pAg is selected in the range of 5 to 10. As a methodof washing with water, one can be selected from the noodle washingmethod, the dialysis method using a diaphragm, the centrifugationmethod, the coagulation settling method, and the ion exchange method. Inthe case of the coagulation settling method, selection can be made from,for example, the method wherein sulfuric acid is used, the methodwherein an organic solvent is used, the method wherein a water-solublepolymer is used, and the method wherein a gelatin derivative is used.

When the emulsion according to the present invention is prepared, inaccordance with the purpose, it is preferable to allow a salt of a metalion to be present, for example, at the time when grains are formed, inthe step of desalting, at the time when the chemical sensitization iscarried out, or before the application. When the grains are doped, theaddition is preferably carried out at the time when the grains areformed; or after the formation of the grains, when the surface of thegrains is modified or when the salt of a metal ion is used as a chemicalsensitizer; or before the completion of the chemical sensitization. Asto the doping of grains, selection can be made from a case in which thewhole grains are doped, one in which only the core parts of the grainsare doped, one in which only the shell parts of the grains are doped,one in which only the epitaxial parts of the grains are doped, and onein which only the substrate grains are doped. For example, Mg, Ca, Sr,Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os,Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb, and Bi can be used. These metals canbe added if they are in the form of a salt that is soluble at the timewhen grains are formed, such as an ammonium salt, an acetate, a nitrate,a sulfate, a phosphate, a hydroxide, a six-coordinate complex, and afour-coordinate complex. Examples include CdBr₂, CdCl₂, Cd(NO₃)₂,Pd(NO₃)₂, Pb(CH₃COO)₂, K₃[Fe(CN)₆], (NH₄)₄[Fe(CN)₆], K₃IrCl₆,(NH₄)₃RhCl₆, and K₄Ru(CN)₆. As a ligand of the coordination compound,one can be selected from halo, aquo, cyano, cyanate, thiocyanate,nitrosyl, thionitrosyl, oxo, and carbonyl. With respect to these metalcompounds, only one can be used, but two or more can also be used incombination.

In some cases, a method wherein a chalcogen compound is added during thepreparation of the emulsion, as described in U.S. Pat. No. 3,772,031, isalso useful. In addition to S, Se, and Te, a cyanate, a thiocyanate, aselenocyanate, a carbonate, a phosphate, or an acetate may be present.

The silver halide grains according to the present invention can besubjected to at least one of sulfur sensitization, seleniumsensitization, tellurium sensitization (these three are called chalcogensensitization, collectively), noble metal sensitization, and reductionsensitization, in any step of the production for the silver halideemulsion. A combination of two or more sensitizations is preferable.Various types of emulsions can be produced, depending on the steps inwhich the chemical sensitization is carried out. There are a typewherein chemical sensitizing nuclei are embedded in grains, a typewherein chemical sensitizing nuclei are embedded at parts near thesurface of grains, and a type wherein chemical sensitizing nuclei areformed on the surface. In the emulsion according to the presentinvention, the location at which chemical sensitizing nuclei aresituated can be selected in accordance with the purpose, and generallypreferably at least one type of chemical sensitizing nucleus is formednear the surface.

Chemical sensitizations that can be carried out preferably in thepresent invention are chalcogen sensitization and noble metalsensitization, which may be used singly or in combination; and thechemical sensitization can be carried out by using active gelatin asdescribed by T. H. James in “The Photographic Process,” 4th edition,Macmillan, 1997, pages 67 to 76, or by using sulfur, selenium,tellurium, gold, platinum, palladium, or iridium, or a combination ofthese sensitizing agents, at a pAg of 5 to 10, a pH of 5 to 8, and atemperature of 30 to 80° C., as described in Research Disclosure, Item12008 (April 1974); Research Disclosure, Item 13452 (June 1975);Research Disclosure, Item 307105 (November 1989); U.S. Pat. Nos.2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018, and3,904,415, and British Patent No. 1 315 755.

In the sulfur sensitization, an unstable sulfur compound is used, andspecifically, thiosulfates (e.g. hypo), thioureas (e.g.diphenylthiourea, triethylthiourea, and allylthiourea), rhodanines,mercaptos, thioamides, thiohydantoins, 4-oxooxazolidin-2-thions, di- orpoly-sulfides, polythionic acids, and elemental sulfur, and knownsulfur-containing compounds described in U.S. Pat. Nos. 3,857,711,4,266,018, and 4,054,457, can be used. In many cases, sulfursensitization is used in combination with noble metal sensitization.

A preferable amount of a sulfur sensitizing agent used for the silverhalide grains accrding to the present invention is 1×10⁻⁷ to 1×10⁻³ mol,and more preferably 5×10⁻⁷ to 1×10⁻⁴ mol, per mol of the silver halide.

In the selenium sensitization, known unstable selenium compounds areused, such as those described, for example, in U.S. Pat. Nos. 3,297,446and 3,297,447, specific such selenium compounds are colloidal metalselenium, selenoureas (e.g. N,N-dimethylselenourea andtetramethylselenourea), selenoketones (e.g. selenoacetone), selenoamides(e.g. selenoacetamide), selenocarboxylic acids and esters,isoselenocyanates, selenides (e.g. diethylselenides andtriphenylphosphine selenide), and selenophosphates (e.g.tri-p-tolylselenophosphate). In some cases, preferably the seleniumsensitization is used in combination with one or both of sulfursensitization and noble metal sensitization.

The amount of the selenium sensitizing agent to be used varies dependingon the selenium compound, the silver halide grains, the chemicalripening conditions, and the like that are used, and the amount isgenerally of the order of 10⁻⁸ to 10⁻⁴ mol, and preferably 10⁻⁷ to 10⁻⁵mol, per mol of the silver halide.

As the tellurium sensitizing agent used in the present invention,compounds described in Canadian Patent No. 800 958, British Patent Nos.1 295 462 and 1 396 696, and JP-A-2-333819 and 3-131598 can be used, andspecific tellurium sensitizing agents include colloidal tellurium,telluroureas (e.g. tetramethyltellurourea,N-carboxylethyl-N′,N′-dimethyltellurourea, andN,N′-dimethylethylenetellurourea), isotellurocyanates, telluroketones,telluroamides, tellurohydrazides, telluroesters, phosphine tellurides(e.g. tributylphosphine telluride and butylisopropylphosphinetelluride), and other tellurium compounds (e.g. potassium tellurocyanateand sodium telluropentathionate).

The amount of the tellurium sensitizing agent to be used is of the orderof generally 10⁻⁷ to 5×10⁻² mol, and more preferably 5×10⁻⁷ to 10⁻³ mol,per mol of the silver halide.

In the noble metal sensitization, a salt of a noble metal, such asplatinum, gold, palladium, and iridium, can be used, and specificallygold sensitization, palladium sensitization, and a combination thereofare particularly preferable. In the case of gold sensitization, a knowncompound, such as chloroauric acid, potassium chloroaurate, potassiumauriothiocyanate, gold sulfide, and gold selenide, can be used. Thepalladium compound means salts of divalent or tetravalent palladiumsalt. A preferable palladium compound is represented by R₂PdX₆ orR₂PdX₄, wherein R represents a hydrogen atom, an alkali metal atom, oran ammonium radical; and X represents a halogen atom, i.e. a chlorineatom, a bromine atom, or an iodine atom.

Specifically, K₂PdCl₄, (NH₄)₂PdCl₆, NaPdCl₄, (NH₄)₂PdCl₄, Li₂PdCl₄,Na₂PdCl₆, or K₂PdBr₄ is preferable. Preferably a gold compound and apalladium compound are used in combination with a thiocyanate or aselenocyanate.

Preferably the emulsion according to the present invention is used incombination with gold sensitization. A preferable amount of the goldsensitizing agent is 1×10⁻⁷ to 1×10⁻³ mol, and more preferably 5×10⁻⁷ to5×10⁻⁴ mol, per mol of the silver halide. A preferable amount of thepalladium compound is in the range of 5×10⁻⁷ to 1×10⁻³ mol. A preferableamount of the thiocyan compound and the selenocyan compound is in therange of 1×10⁻⁶ to 5×10⁻² mol.

Preferably that the silver halide emulsion according to the presentinvention is subjected to reduction sensitization during the formationof the grains, after the formation of the grains but before the chemicalsensitization, or during or after the chemical sensitization.

Herein, the reduction sensitization can be selected from a methodwherein a reduction sensitizer is added to a silver halide emulsion; amethod called silver ripening, wherein the growth or ripening is made inan atmosphere having a pAg as low as 1 to 7; and a method called high-pHripening, wherein the growth or ripening is made in an atmosphere havinga pH as high as 8 to 11. Two or more methods can also be used incombination.

The method wherein a reduction sensitizer is added is preferable,because the level of reduction sensitization can be adjusted subtly.

As the reduction sensitizer, known reduction sensitizers can be selectedand used, such as stannous salts, ascorbic acid and its derivatives,amines and polyamines, hydrazine and its derivatives, formamidinesufinicacid, silane compounds, and boran compounds; and two or more compoundscan be used in combination. As the reduction sensitizer, preferablecompounds are stannous chloride, aminoiminomethanesulfinic acid(popularly called thiourea dioxide), dimethylamineboran, and ascorbicacid and its derivatives. Since the amount of the reduction sensitizerto be added depends on the conditions of the production of the emulsion,the amount must be selected, but preferably it is in the range of 10⁻⁷to 10⁻³ mol per mol of the silver halide.

The chemical sensitization can be carried out in the presence of aso-called chemical sensitization auxiliary. As a useful chemicalsensitization auxiliary, a compound is used that is known to suppressfogging and to increase the sensitivity in the process of chemicalsensitization, such as azaindene, azapyridazine, and azapyrimidine.Examples of chemical sensitization auxiliary improvers are described inU.S. Pat. Nos. 2,131,038, 3,411,914, and 3,554,757, JP-A-58-126526, andby G. F. Duffin in “Photographic Emulsion Chemistry” mentioned above,pages 138 to 143.

Preferably, an oxidizing agent for silver is added during the process ofthe production of the emulsion according to the present invention. Theoxidizing agent for silver refers to a compound that acts on metalsilver to convert it to silver ions. Particularly useful is a compoundthat converts quite fine silver grains, which are concomitantly producedduring the formation of silver halide grains and during the chemicalsensitization, to silver ions. The thus produced silver ions may form asilver salt that is hardly soluble in water, such as a silver halide,silver sulfide, and silver selenide, or they may form a silver salt thatis readily soluble in water, such as silver nitrate. The oxidizing agentfor silver may be inorganic or organic. Example inorganic oxidizingagents include ozone, hydrogen peroxide and its adducts (e.g. NaBO₂,H₂O₂.H₂O, 2NaCO₃.H₂O₂, Na₄P₂O₇. H₂O₂, and 2NaSO₄.H₂O₂.2H₂O); oxygen acidsalts, such as peroxyacid salts (e.g. K₂S₂O₈, K₂C₂O₆, and K₂P₂O₈),peroxycomplex compounds (e.g. K₂[Ti(O₂)C₂O₄].3H₂O,4K₂SO₄.Ti(O₂)OH.SO₄.2H₂O, and Na₃[VO(O₂)(C₂O₄)₂].6H₂O), permanganates(e.g. KMnO₄), and chromates (e.g. K₂CrO₇); halogen elements, such asiodine and bromine; perhalates (e.g. potassium periodate), salts ofmetals having higher valences (e.g. potassium hexacyanoferrate(III), andthiosulfonates.

Examples of the organic oxidizing agents include quinones, such asp-quinone; organic peroxides, such as peracetic acid and perbenzoicacid; and compounds that can release active halogen (e.g.N-bromosuccinimido, chloramine T, and chloramine B).

Preferable oxidizing agents used in the present invention are suchinorganic oxidizing agents as ozone, hydrogen peroxide and its adducts,halogen elements, and thiosulfonates, and such organic oxidizing agentsas quinones. Use of a combination of the above reduction sensitizationwith the oxidizing agent for silver is a preferable mode. Use is made ofone selected from a method wherein after an oxidizing agent is used,reduction sensitization is carried out; a method wherein after reductionsensitization is carried out, an oxidizing agent is used; and a methodwherein an oxidizing agent and a reduction sensitizer are presentsimultaneously. These methods can be used in the step of forming grainsor in the step of chemical sensitization, which step will be chosen.

In the photographic emulsion used in the present invention, variouscompounds can be incorporated for the purpose of preventing foggingduring the process of the production of the photographic material,during the storage of the photographic material, or during thephotographic processing, or for the purpose of stabilizing thephotographic performance. That is, compounds known as antifoggants orstabilizers can be added, such as thiazoles including benzothiazoliumsalts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles,bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles,mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles,benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (particularly1-phenyl-5-mercaptotetrazole), mercaptopyrimidine, mercaptotriazine;thioketo compounds, such as oxazolinthione; and azaindenes, such astriazaindenes; tetraazaindenes (particularly4-hydroxy-6-methyl-1,3,3a,7-tetraazaindenes), and pentaazaindenes. Forexamples, those described in U.S. Pat. Nos. 3,954,474 and 3,982,947, andJP-B-62-28660, can be used. A preferable compound is a compounddescribed in Japanese Patent Application No. 62-47225. In accordancewith the purpose, the antifoggant and the stabilizer can be added atvarious times, for example, before the formation of the grains, duringthe formation of the grains, after the formation of the grains, in thestep of washing with water, at the time of dispersion after the washingwith water, before the chemical sensitization, during the chemicalsensitization, after the chemical sensitization, and before theapplication. In addition to the case wherein the antifoggant and thestabilizer are added during the preparation of the emulsion, so that theantifogging effect and the stabilizing effect, which are their essentialeffects, may be achieved, they can be used for various other purposes,for example, for controlling the habit of the crystals of the grains,for making the grain size small, for reducing the solubility of thegrains, for controlling the chemical sensitization, and for controllingthe arrangement of the dyes.

When the photosensitive silver halide used in the present invention ismade to have color sensitivities of green sensitivity, red sensitivity,and infrared sensitivity, the photosensitive silver halide emulsion isspectrally sensitized with methine dyes or the like. If required, theblue-sensitive emulsion may be spectrally sensitized in the blue region.

Dyes that can be used include a cyanine dye, a merocyanine dye, acomposite cyanin dye, a composite merocyanine dye, a halopolar cyaninedye, a hemicyanine dye, a styryl dye, and a hemioxonol dye. Particularlyuseful dyes are those belonging to a cyanine dye, a merocyanine dye, anda composite merocyanine dye. In these dyes, any of nuclei generally usedin cyanine dyes as base heterocyclic ring nuclei can be applied. Thatis, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, apyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazolenucleus, an imidazole nucleus, a tetrazole nucleus, and a pyridinenucleus; and a nucleus formed by fusing an cycloaliphatic hydrocarbonring or an aromatic hydrocarbon ring to these nuclei, that is, 5- to6-heterocyclic ring nuclei, such as an indolenine nucleus, abenzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, anaphthooxazole nucleus, a benzothiazole nucleus, a naphthothiazolenucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a rhodaninenucleus, and a thiobarbituric acid nucleus, can be applied. These nucleimay be substituted on the carbon atom. Specifically, sensitizing dyesdescribed, for example, in U.S. Pat. No. 4,617,257 and JP-A-59-180550,JP-A-64-13546, JP-A-5-45828, and JP-A-5-45834 can be mentioned. Inaddition, specific examples include thermally decolorant sensitizingdyes described in JP-A-59-180550, JP-A-60-140335 and Journal of Research& Disclosure, the June issue, pp12-13 (1978) (RD-17029).

In the merocyanine dye or the composite merocyanine dye, as a nucleushaving a ketomethylene structure, a 5- to 6-membered heterocyclic ringnucleus, such as a pyrazolin-5-one nucleus, a thiohydantoine nucleus, a2-thiooxazolidin-2,4-dione nucleus, a thiazolidin-2,4-dione nucleus, arhodanine nucleus, and a thiobarbituric acid nucleus, can be applied.

These dyes can be used singly or in combination, and a combination ofthese sensitizing dyes is often used, particularly for the purpose ofadjusting the wavelength of the spectral sensitivity, and for thepurpose of supersensitization. Typical examples thereof are described inU.S. Pat. Nos. 2,688,545, 3,397,060, 2,977,229, 3,522,052, 3,527,64,3,617,293, 3,628,964, 3,672,989, 3,679,428, 3,703,377, 3,769,301,3,814,609, 3,837,862, and 4,026,707, British Patent Nos. 1 344 218 and 1507 803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

Together with the sensitizing dye, a dye having no spectral sensitizingaction itself, or a compound that does not substantially absorb visiblelight and that exhibits supersensitization, may be included in theemulsion (e.g. those described, for example, in U.S. Pat. No. 3,615,641and JP-A-63-23145).

The time when these sensitizing dyes are added to the emulsion may be atany stage of the preparation of the emulsion that is known to be useful.

Most usually, the sensitizing dye is added at a time after thecompletion of chemical sensitization but before the application, but thesensitizing dye may be added at the same time as the addition of thechemical sensitizer, to carry out spectral sensitization and chemicalsensitization simultaneously, as described in U.S. Pat. Nos. 3,628,969and 4,225,666, or the sensitizing dye may be added before the chemicalsensitization, as described in JP-A-58-113928. Further, the sensitizingdye may be added before the completion of the precipitation of thesilver halide grains, to start the spectral sensitization. Further, thesensitizing dye may be added before or after the formation of nuclei ofthe silver halide grains, in accordance with U.S. Pat. Nos. 4,183,756and 4,225,666, or it may be added in portions, such that part of thesensitizing dye is added before the chemical sensitization, and the restis added after the chemical sensitization.

Further, these sensitizing dyes and supersensitizing dyes may be addedin the form of a solution of an organic solvent, such as methanol, or inthe form of a dispersion of gelatin, or in the form of a solution of asurface-active agent.

Generally the amount of the sensitizing dye to be added is of the orderof 4×10⁻⁶ to 8×10⁻³ mol per mol of the silver halide, but when thesilver halide grain size is 0.2 to 1.2 μm, which is more preferable, theamount of the sensitizing dye to be added is more effectively about5×10⁻⁵ to 2×10⁻³ mol per mol of the silver halide.

To the photographic material related to the present technique, may beadded the above-mentioned various additives, and also other variousadditives in accordance with the purpose.

These additives are described in more detail in Research Disclosure,Item 17643 (December 1978); Research Disclosure, Item 18176 (November1979); and Research Disclosure, Item 307105 (November 1989), and theparticular parts are given below in a Table.

Additive RD 17643 RD 18716 Rd 307105 1 Chemical p. 23 p. 648 (right p.996 sensitizers column) 2 Sensitivity- — p. 648 (right — enhancingagents column) 3 Spectral pp. 23- pp. 648 (right pp. 996-998 sensitizersand 24 column)-649 Supersensitizers (right column) 4 Brightening p. 24pp. 647 (right p. 998 agents column) 5 Light absorbers, pp. 25- pp. 649(right p. 1003 Filter dyes, and 26 column)-650 UV Absorbers (leftcolumn) 6 Binders p. 26 p. 651 pp. 1003-1004 7 Plasticizers and p. 27 p.650 p. 1006 Lubricants 8 Coating aids and pp. 26- p. 650 pp. 1005Surfactants 27 (left)-1006 (right) 9 Antistatic p. 27 p. 650 (right pp.1006-1007 agents column) 10 Antifogging pp. 24— p.649 pp. 998-1000agents and 25 Stabilizers 11 Anti-staining p. 25 p. 650 (left to agents(right right) column) 12 Image-dye p. 25 stabilizers 13 Hardeners p. 26p. 651 (left pp. 1004 column) (right)-1005 (left)

In addition to the above hardeners, other hardeners are described, forexample, in U.S. Pat. No. 4,678,739, 41st column; U.S. Pat. No.4,791,042, and JP-A-59-116655, 62-245261, 61-18942, and 4-218044. Morespecifically, aldehyde hardeners (e.g. formaldehyde), aziridinehardeners, epoxy hardeners, vinyl sulfone hardeners (e.g.N,N′-ethylene-bis(vinylsulfonylacetamide)ethane), N-methylol hardeners(e.g. dimethylol urea), or polymer hardeners (e.g. compounds described,for example, in JP-A-62-234157) can be mentioned.

These hardeners are used in an amount of 0.001 to 1 g, and preferably0.005 to 0.5 g, per g of the coated gelatin. The layer into which thehardeners are added may be any of layers that constitute thephotographic material (another name, a photographic element) or thedye-fixing material (another name, a dye-fixing element or an imagereceiving element), or the hardener may be divided into two or moreparts, which are added into two or more layers.

In the photographic material of the present invention, a matting agentcan be used for the purpose of adhesion prevention, improvement ofslipping property, matting, etc. Example matting agents icnclude silicondioxide, polyolefins, polymethacrylates, and the like described inJP-A-61-88256, page 29, as well as compounds, including benzoguanamineresin beads, polycarbonate resin beads, ABS resin beads, and the like,described in JP-A-63-274944 and 63-274952. Other matting agentsdescribed in the above RD can be used. These matting agents are addedinto the uppermost layer (protective layer), and also into a lower layerif required.

Further, the constitutional layers of a heat-developable photographicmaterial may contain a heat solvent, an antifoaming agent, agerm-proofing agent, a mildew-proofing agent, colloidal silica, etc.Specific examples of these additives are described, for example, inJP-A-61-88256, pages 26 to 32; JP-A-3-11338, and JP-B-51-51496.

In the constitutional layers of the photographic material of the presentinvention, use can be made of various surface-active agents for variouspurposes of, for example, serving as a coating aid, improvingreleasability and slipping property, preventing electrification, orpromoting development. Specific examples of the surface-active agentsare described, for example, in the above Research Disclosures andJP-A-62-173463 and 62-183457. In the case of a heat-developablephotographic material, also preferably an organofluoro compound iscontained in the constitutional layer, for example, for the purposes ofimproving slipping properties, preventing electrification, and improvingreleasability. Typical examples of the organofluoro compound arehydrophobic fluoro compounds, including solid fluoro compound resins,such as ethylene tetrafluoride resins; oily fluoro compounds, includingfluoro oils; or fluorine-containing surface-active agents described, forexample, in JP-B-57-9053, 8th column to the 17th column, andJP-A-61-20944 and 62-135836.

In the photographic material of the present invention, known antifadingagents can be used. Example organic antifading agents includehydroquinones, 5-hydroxychromans, 5-hydroxycoumarans, paraalkoxyphenols,hindered phenols, including bisphenols; gallic acid derivatives,methylenedioxybenzenes, aminophenols, hindered amines, and ether orester derivatives produced by silylating or alkylating the phenolichydroxyl group of these compounds. Further, metal complexes, representedby (bissalicylaldoximato)nickel complex and(bis-N,N-dialyldithiocarbamato)nickel complex, can also be used.

To prevent a yellow dye image from being deteriorated by heat, humidity,and light, the addition of a compound having both the structures of ahindered amine and a hindered phenol in the same molecule, as describedin U.S. Pat. No. 4,268,593, gives a good result. Further, to prevent amagenta dye image from being deteriorated particularly by light,spiroindanes described in JP-A-56-159644, and chromans substituted witha hydroquinone diether or monoether, described in JP-A-55-89835, give agood result.

In the constitutional layers of the photographic material of the presentinvention, various antifoggants or photographic stabilizers and theirprecursors can be used. Specific examples thereof are compoundsdescribed, for example, in the above-mentioned Research Disclosures,U.S. Pat. Nos. 5,089,378, 4,500,627, and 4,614,702, JP-A-64-13546 (pages7 to 9, 57 to 71, and 81 to 97), U.S. Pat. Nos. 4,775,610, 4,626,500,and 4,983,494, JP-A-62-174747, 62-239148, 63-264747, 1-150135, 2-110557,and 2-178650, and Research Disclosure No. 17 643 (1978), pages 24 to 25.

These compounds are preferably used in an amount of 5×10⁻⁶ to 1×10⁻¹mol, and more preferably 1×10⁻⁵×1×10⁻² mol, per mol of silver.

Suitable bases that can be used in the present invention include asynthetic plastic film, for example, made of polyolefins, such aspolyethylenes and polypropylenes, polycarbonates, cellulose acetates,polyethylene terephthalates, polyethylene naphthalates, and polyvinylchlorides; a paper base, for example, made of photographic base paper,printing paper, baryta paper, and resin-coated paper; a base formed byproviding the above plastic film with a reflective layer; and a basedescribed in JP-A-62-253159, pages 29 to 31.

Those described in the above Research Disclosure No. 17643, page 28;Research Disclosure No. 18716, page 647, right column, to page 648, leftcolumn; and Research Disclosure No. 307105, page 879, are preferablyused. These bases may be subjected to heat treatment at or below Tg, asdescribed in U.S. Pat. No. 4,141,735, so that they may be hardlycore-set. The surface of the bases may be surface-treated, to improvethe adhesion between the base and the emulsion undercoat layer. In thepresent invention, the surface treatment can be carried out by glowdischarge treatment, ultraviolet-ray-irradiation treatment, coronatreatment, or flame treatment.

Further, bases described in Kochi Gijutsu No. 5 (published by AzutekkuYugen-kaisha, Mar., 22, 1991), pages 44 to 149, can also be used.

Transparent bases made, for example, of polyethylenedinaphthalenedicarboxylates, and bases produced by coating these transparent baseswith a transparent magnetic product, can also be used.

In a heat-developable photographic material, in order to obtain aconstant image all the time against changes in the processingtemperature and the processing time at the time of development, variousdevelopment inhibitors can be used. Herein, the term “a developmentinhibitor” means a compound that neutralizes bases quickly or reactsquickly with bases after suitable development, to lower the baseconcentration in the film, to stop the development; or a compound thatinteracts with silver and silver salts, to inhibit the development.Specific examples include acid precursors that release an acid whenheated, electrophilic compounds that undergo a substitution reactionwith coexisting bases when heated, nitrogen-containing heterocycliccompounds, mercapto compounds, and their precursors. Details aredescribed in JP-A-62-253159, pages 31 to 32.

When the photographic material of the present invention is used as aheat-developable photographic material, to supply a base, a methodwherein a base is generated from a base precursor, is preferable.

Preferable base precursors used in the present invention include a saltof a base with an organic acid that is decarboxylated when heated; acompound that is decomposed by such a reaction as an intramolecularnucleophilic substitution reaction, Lossen rearrangement, or Beckmannrearrangement, to release amines; a compound that undergoes somereaction when heated, to release a base; and a compound that undergoeshydrolysis or a complex formation reaction, to generate a base. Examplesof the above base precursor that generates a base when heated includebases of trichloroacetic acid described, for example, in British PatentNo. 998 959; bases of α-sulfonylacetic acid that are further improved instability, as described in U.S. Pat. No. 4,060,420; bases of propiolicacid described in Japanese Patent Application No. 58-55700;2-carboxycarbodiamide derivatives described in U.S. Pat. No. 4,088,496;salts of heat-decomposable acids that are formed using, in addition toan organic base, an alkali metal or an alkali earth metal (JapanesePatent Application No. 58-69597); hydroxamcarbamates that use Lossenrearrangement, as described in Japanese Patent Application No. 58-43860;and aldoximecarbamates that produce nitrile when heated, as described inJapanese Patent Application No. 58-31614.

Also useful are base precursors described, for example, in BritishPatent Nos. 998 945 and 2 079 480, JP-A-50-226225, U.S. Pat. Nos.3,220,846, 4,514,493, and 4,657,848, and Kochi Gijutsu No. 5 (publishedby Azutekku Yugen-kaisha, Mar. 22, 1991), pages 55 to 86.

Examples methods of exposing the photographic material of the presentinvention with light and recording the image, include a method wherein alandscape, a man, or the like is directly photographed by a camera orthe like; a method wherein a reversal film or a negative film is exposedto light using, for example, a printer, or an enlarging apparatus; amethod wherein an original picture is subjected to scanning exposurethrough a slit by using an exposure system of a copying machine or thelike; a method wherein light-emitting diodes and various lasers (e.g.laser diodes and gas lasers) are allowed to emit light, to carry outscanning exposure through image information and electrical signals(methods described, for example, in JP-A-2-129625 and Japanese PatentApplication Nos. 3-338182, 4-9388, and 4-281442); and a method whereinimage information is outputted to an image display apparatus, such as aCRT, a liquid crystal display, an electroluminescence display, and aplasma display, and exposure is carried out directly or through anoptical system.

Light sources that can be used for recording an image on thephotographic material, as mentioned above, include natural light andlight sources and exposure methods described in U.S. Pat. No. 4,500,626,56th column, and JP-A-2-53378 and 2-54672, such as a tungsten lamp, alight-emitting diode, a laser light source, and a CRT light source.

Image-wise exposure can be carried out by using a wavelength-convertingelement that uses a nonlinear optical material and a coherent lightsource, such as laser rays, in combination. Herein the term “nonlinearoptical material” refers to a material that can develop nonlinearity ofthe electric field and the polarization that appears when subjected to astrong photoelectric field, such as laser rays, and inorganic compounds,represented by lithium niobate, potassium dihydrogenphosphate (KDP),lithium iodate, and BaB204; urea derivatives, nitroaniline derivatives,nitropyridine-N-oxide derivatives, such as3-methyl-4-nitropyridine-N-oxide (POM); and compounds described inJP-A-61-53462 and 62-210432 can be preferably used. As the form of thewavelength-converting element, for example, a single crystal opticalwaveguide type and a fiber type are known, both of which are useful.

The above image information can employ, for example, image signalsobtained from video cameras, electronic still cameras, and the like;television signals, represented by Nippon Television Singo Kikaku(NTSC); image signals obtained by dividing an original picture into anumber of picture elements by a scanner or the like; and an imageproduced by a computer, represented by CG or CAD.

The color-developing agent of the present invention can be used for allsilver halide photographic materials, including color negatives, colorpapers, X-ray photographic materials and photomechanical reproductionmaterials for color instant photography and color reversal, and X-rayphotographic materials and reproduction photographic materials forforming color images. Further, the color-developing agent of the presentinvention can be added into a silver halide photographic material, andalso into a processing solution. The color-developing agent for use inthe present invention is contained in at least one hydrophilic colloidlayer provided on a support, when it is used in a silver halidelight-sensitive material. As a silver halide light-sensitive materialcontaining a color-developing agent for use in the present invention, acolor diffusion transfer silver halide photographic light-sensitivematerial is preferable.

If the color-developing agent for use in the present invention is addedinto a silver halide photographic material, the development can becarried out by heating treatment or activator treatment.

The heating treatment of photographic materials is known in the art, andheat-developable photographic materials and the process thereof aredescribed, for example, in “Shashin Kogaku no Kiso” (published byCorona-sha, 1979), pages 553 to 555; “Eizo Joho” (published April 1978),page 40; “Nebletts Handbook of Photography and Reprography,” 7th edition(Van Nostrand and Reinhold Company), pages 32 to 33; U.S. Pat. Nos.3,152,904, 3,301,678, 3,392,020, and 3,457,075, British Patent Nos. 1131 108 and 1 167 777, and Research Disclosure (June 1978), pages 9 to15 (RD-17029).

The activator treatment refers to a treatment wherein a color developingagent is built in a photographic material and the photographic materialis developed with a processing solution free from any color-developingagent. In this case, the processing solution is characterized in that itdoes not contain a color-developing agent, which is normally containedas a development processing solution component, but the processingsolution may contain other components (e.g. an alkali and an auxiliarydeveloping agent). Examples of the activator treatment are shown inknown publications, such as European Patent Nos. 545 491(A1) and 565165(A1).

In the present invention, the term “a developing solution” means aprocessing solution containing a color-developing agent or a processingsolution not containing a developing agent (for activator).

Processing materials and processing methods used in the case of theactivator treatment in the present invention will now be described indetail. In the present invention, the photographic material is developed(silver development/cross oxidation of the built-in color-developingagent), desilvered, washed with water, and stabilized. In some cases,after the washing with water or the stabilizing processing, a treatmentof alkalinization for color formation intensification (alkali treatment)is carried out.

When the photographic material of the present invention is developedwith a developing solution, preferably the developing solution containsa compound that functions as a developing agent of silver halides and/orallows the developing agent oxidation product resulting from the silverdevelopment to cross-oxidize the color-developing agent built in thephotographic material (auxiliary developing agent). Preferably,pyrazolidones, dihydroxybenzenes, reductones, and aminophenols are used,and particularly preferably pyrazolidones are used.

Among pyrazolidones, 1-phenyl-3-pyrazolidones are preferable, and theyinclude 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone,1-phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone,1-phenyl-4,4-dihydroxydimethyl-3-pyrazolidone,1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone,1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone,1-p-chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone,1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone,1-phenyl-2-acetyl-3-pyrazolidone,1-phenyl-2-hydroxymethyl-5-phenyl-3-pyrazolidone, and1-(2-chlorophenyl)-4-hydroxymethyl-4-methyl-3-pyrazolidone.

Dihydroxybenzenes include hydroquinone, chlorohydroquinone,bromohydroquinone, isopropylhydroquinone, methylhydroquinone,2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone,2,5-dimethylhydroquinone, and potassium hydroquinonemonosulfonate.

Reductones include N-methyl-p-aminophenol,N-(β-hydroxyethyl)-p-aminophenol, N(4-hydroxyphenyl)glycine, and2-methyl-p-aminophenol.

Although these compounds are generally used singly, use of two or moreof them in combination is also preferable, to enhance the developmentand cross oxidation activity.

The amount of these compounds to be used in the developing solution isgenerally 2.5×10⁻⁴ to 0.2 mol/liter, preferably 0.0025 to 0.1 mol/liter,and more preferably 0.001 to 0.05 mol/liter.

Example preservatives for use in the developing solution according tothe present invention include sodium sulfite, potassium sulfite, lithiumsulfite, formaldehyde sodium bisulfite, and hydroxylamine sulfate, whichare preferably used in an amount in the range of 0.1 mol/liter or below,and more preferably 0.001 to 0.02 mol/liter. If a high-silver-chlorideemulsion is used in the photographic material, the above compound isused in an amount of generally 0.001 mol/liter or below, and preferablyit is not used at all in some cases.

In the present invention, instead of the above hydroxylamine or sulfiteions, an organic preservative can be preferably used.

Herein the term “organic preservatives” refers generally to organiccompounds that reduce the deterioration speed of the above developingagent when added to the developing solution. That is, organicpreservatives are organic compounds that have a function of preventingdeveloping agents from being oxidized with air or the like; andparticularly effective organic preservatives are other hydroxylaminederivatives (excluding hydroxylamine), hydroxamic acids, hydrazines,phenols, α-hydroxyketones, α-aminoketones, saccarides, monoamines,diamines, polyamines, quaternary ammoniums, nitroxy radicals, alcohols,oximes, diamide compounds, and fused-ring-type amines. These aredescribed, for example, in JP-A-63-4235, 63-5341, 63-30845, 63-21647,63-44655, 63-46454, 63-53551, 63-43140, 63-56654, 63-58346, 63-43138,63-146041, 63-44657, and 63-44656, U.S. Pat. Nos. 3,615,503 and2,494,903, and JP-B-48-30496. Further, other reservatives that may becontained, if required, include, for example, various metals describedin JP-A-57-44148 and 57-53749, salicylic acids described inJP-A-59-180588, alkanolamines described in JP-A-54-3532,polyethyleneamines described in JP-A-61-94349, and aromatic polyhydroxycompounds described in U.S. Pat. No. 3,746,544. In particular,preferably contained are alkanolamines described in JP-A-4-97355, pages631 to 632, and dialkylhydroxylamines described therein, pages 627 to630. Further, it is also preferable to use a combination ofdialkylhydroxylamines and/or hydrazine derivatives with alkanolamines,or a combination of α-amino acids, represented by glycine, withdialkylhydroxylamines, as described in European Patent No. 530 921(A1).

These compounds are preferably used in an amount of 1×10⁻³ to 5×10⁻¹mol, and more preferably 1×10⁻² to 2×10⁻¹ mol, per liter of thedeveloping solution.

In the present invention, the developing solution contains halide ions,such as chloride ions, bromide ions, and iodide ions. Preferably, when ahigh silver-chloride emulsion is used, chloride ions are contained in anamount of 3.5×10⁻³ to 3.0×10⁻¹ mol/liter, and more preferably 1×10⁻² to2×10⁻¹ mol/liter, and/or bromide ions in an amount of 0.5×10⁻⁵ to1.0×10⁻³ mol/liter, and more preferably 3.0×10⁻⁵ to 5×10⁻⁴ mol/liter.

Herein the halide ions may be added directly to the developing solution,or they may be dissolved out from the photographic material into thedeveloping solution during the development processing.

If the halide ions are added to the developing solution, the halide ionsource may be a sodium salt, a potassium salt, an ammonium salt, alithium salt, or a magnesium salt, of the halide ion.

When the halide ions are dissolved out from the light-sensitivematerial, the halide ions are supplied mainly from the silver halideemulsion, but they may also be supplied from some other source.

The developing solution used in the present invention preferably has apH of 8 to 13, and more preferably 9 to 12.

To retain the above pH, it is preferable to use various buffers,examples of which are carbonates, phosphates, brorates, tetraborates,hydroxybenzoates, glycinates, N,N-dimethylglycinates, leucinates,norleucinates, guaninates, 3,4-dihydroxyphenylalaninates, alaninates,aminobutylates, 2-amino-2-methyl-1,3-propandiol salts, valerates,prolinates, trishydroxylaminomethane salts, and lysinates. Inparticular, carbonates, phosphates, tetraborates, and hydroxybenzoatesare excellent in solubility and buffering function at a pH in the rangeof 9.0 or over, and when they are added to the developing solution, thephotographic performance is not adversely affected, so that they arepreferably used.

Specific examples of these buffers are lithium carbonate, sodiumcarbonate, potassium carbonate, potassium bicarbonate, tripotassiumphosphate, trisodium phosphate, dipotassium phosphate, disodiumphosphate, potassium borate, sodium borate, sodium tetraborate,potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), andpotassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).

The amount of the buffers to be added to the developing solution ispreferably 0.05 mol/liter or over, and particularly preferably 0.1 to0.4 mol/liter.

In addition, in the developing solution, as a sediment-preventive agentagainst calcium and magnesium, or as an agent for stabilizing thedeveloping solution, various chelating agents can be used. Examples arenitrilotriacetic acid, diethylenetriaminepentaacetic acid,ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid,ethylenediamine-N,N,N′,N′-tetramethylenesulfonic acid,1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraaceticacid, ethylenediamine orthohydroxyphenylacetic acid,2-phosphonobutane-1,2,4-tricarboxylic acid,1-hydroxyethylidene-1,1-diphosphonic acid, and1,2-dihydroxybenzene-4,6-disulfonic acid, and their alkali metal salts.Two or more of these chelating agents may be used in combination, ifnecessary.

With respect to the amount of these chelating agents to be added,preferably the amount is enough to sequester the metal ions in thedeveloping solution, and, for example, these chelating agents are usedin an amount in the order of 0.1 to 10 g per liter.

In the present invention, if required, an arbitrary antifoggant can beadded. As the antifoggant, nitrogen-containing heterocyclic compounds,and alkali metal halide, such as sodium chloride, potassium bromide, andpotassium iodide, are used. Typical examples of the nitrogen-containingheterocyclic compounds are benzotriazole, 5-nitrobenzotriazole,5-methylbenzotriazole, 5-nitrobenzimidazole, 5-nitroindazole,2-thiazolylbenzimidazole, indazole, hydroxyazaindolizine, adenine, and1-phenyl-5-mercaptotetrazole, or their derivatives.

The amount of the nitrogen-containing heterocyclic compounds to be addedis 1×10⁻⁵ to 1×10⁻² mol/liter, and preferably 2.5×10⁻⁵ to 1×10⁻³mol/liter.

In the developing solution, if necessary, an arbitrary developmentaccelerator can be added, examples of which are the following compounds:thioether compounds described, for example, in JP-B-37-16088, 37-5987,38-7826, 44-12380, and 45-9019, and U.S. Pat. No. 3,813,247;p-phenylenediamine compounds described in JP-A-52-49829 and 50-15554;quaternary ammonium salts described, for example, in JP-A-50-137726,JP-B-44-30074, and JP-A-56-156826 and 52-43429; amine compoundsdescribed, for example, in U.S. Pat. Nos. 2,494,903, 3,128,182,4,230,796, and 3,253,919, JP-B-41-11431, and U.S. Pat. Nos. 2,482,546,2,596,926, and 3,582,346; and imidazoles and polyalkylene oxidesdescribed, for example, in JP-B-37-16088 and 42-25201 and U.S. Pat. No.3,532,501.

Preferably the developing solution contains a fluorescent whiteningagent. In particular, it is preferable to use4,4-diamino-2,2′-disulfostilbene-type compounds. Specifically,commercially available fluorescent whitening agents, such as compoundsdescribed, for example, in “Senshoku Note,” 19th edition, pages 165 to168, and compounds described in JP-A-4-242943, pages 3 to 7, can beused. The amount to be added is generally 0.1 to 10 g/liter, andpreferably 0.5 to 5 g/liter.

The processing temperature of the developing solution to be applied tothe present invention is 20 to 50° C., and preferably 30 to 45° C. Theprocessing time is 5 sec to 2 min, and preferably 10 sec to 1 min. Withrespect to the replenishing rate, although a small amount is preferable,the replenishing rate is 15 to 600 ml, preferably 25 to 200 ml, and morepreferably 35 to 100 ml, per m² of the photographic material.

The photographic material of the present invention may be in a formhaving an electro-conductive heat-generating element layer, which servesas a heating means for heat processing. In this case, as theheat-generating element, those described, for example, in JP-A-61-145544can be employed.

The heating temperature in the heat development step is generally about65 to 180° C., preferably 70 to 180° C., more preferably 75 to 180° C.,further more preferably 80 to 150° C., and particularly preferably 80 to135° C. The heating time is preferably 0.1 to 120 sec, more preferably0.1 to 60 sec, and particularly preferably 0.1 to 30 sec.

Example heating methods in the development step include one wherein thephotographic material is brought in contact with a heated block orplate; a method wherein the photographic material is brought in contactwith a hot plate, a hot presser, a hot roller, a hot drum, a halogenlamp heater, an infrared lamp heater, or a far-infrared lamp heater; anda method wherein the photographic material is passed through ahigh-temperature atmosphere. As a method wherein the heat-developablephotographic material and a dye-fixing material are placed one upon theother, methods described in JP-A-62-253159 and 61-147244 (page 27) canbe applied.

After the development, a desilvering process can be carried out. Thedesilvering process comprises a fixing process, or both bleachingprocess and a fixing process. When both bleaching and fixing are carriedout, the bleaching process and the fixing process may be carried outseparately or simultaneously (bleach-fixing process). Also, according tothe purpose, the processing may be carried out in a bleach-fixing bathhaving two successive tanks; or the fixing process may be carried outbefore the bleach-fixing process; or the bleach-fixing may be carriedout after the bleach-fixing process.

In some cases, it is preferable to carry out the stabilizing process, tostabilize silver salts and dye images, without carrying out thedesilvering process after the development.

Example bleaching agents for use in the bleaching solution or thebleach-fix solution include, for example, compounds of polyvalentmetals, such as iron(III), cobalt(III), cromium(IV), and copper(II);peracids; qunones; and nitro compounds. Typical compounds are ironchloride, ferricyanides, dichromates, organic complex salts of iron(III)(e.g. metal salts of ethylenediaminetetraacetic acid,diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid,1,3-diaminopropanetetraacetic acid, methylimiodiacetic acid; andaminopolycarboxylic acids and their salts, as described inJP-A-4-365036, pages 5 to 17), persulfates, permanganates, bromates,hydrogen peroxide and compounds releasing thereof (e.g. percarbonic acidand perboric acid), and nitrobenzenes. Among them,ethylenediaminetetraacetatic acid iron(III) complex salts,aminopolycarboxylic acid iron(III) of 1,3-diaminopropanetetraacetateiron(III) complex salts, hydrogen peroxide, persulfates, and the likeare preferred, in view of rapid processing and the prevention ofenviromental pollution. The bleaching solution and bleach-fix solutionthat use these aminopolycarboxylic acid irons(III) are used at a pH of 3to 8, and preferably 5 to 7. The bleaching solution that usespersulfates and hydrogen peroxide is used at a pH of 4 to 11, andpreferably 5 to 10.

In the bleaching solution, the bleach-fix solution, and the bathpreceding them, if required, a bleach-accelerating agent can be used.Specific examples of useful bleach-accelerating agents include compoundshaving a mercapto group or a disulfide bond, as described, for example,in U.S. Pat. No. 3,893,856, West German Patent No. 1 290 812,JP-A-53-95630, and Research Disclosure No. 17129 (July 1978);thiazolidine derivatives described in JP-A-50-140129; thioureaderivatives described in U.S. Pat. No. 3,706,561; iodide salts describedin JP-A-58-16235; polyoxyethylene compounds described in West GermanyPatent No. 2 748 430; and iodide ions and polyamine compounds describedin JP-B-45-9936.

Above all, compounds having a mercapto group or a disulfide group arepreferable, because they are high in accelerating effect. When colorphotographic materials for photography are desilvered, these bleach-accelerating agents are particularly effective.

With respect to the accelerating agent for persulfate bleaching, complexsalts of 2,6-pyridinedicarboxylic acid or 2-pyridinecarboxylic acid withiron (III) ion, as described in JP-A-6-214365 (European Patent No. 0 602600(A1)), are effective. With respect to the accelerating agent forhydrogen peroxide bleaching, metal salts of organic acids, described inJP-B-61-16067 and 61-19024, are effective.

In the bleaching solution, the bleach-fix solution, and the fixingsolution, use can be made of known additives, such as a rehalogenatingagent, including ammonium bromide and ammonium chloride; a pH bufferingagent, including ammonium nitrate, acetic acid, boric acid, citric acidor its salt, tartaric acid or its salt, succinic acid or its salt, andimidazole; and a metal corrosion-preventive agent, including ammoniumsulfate. In particular, it is preferable to contain an organic acid, toprevent bleach stain. The organic acid is a compound having an aciddissociation constant (pKa) of 2 to 7, and specifically acetic acid,succinic acid, citric acid, and propionic acid are preferable.

Example fixing agents for use in the fixing solution and the bleach-fixsolution include thiosulfates, thiocyanates, thioureas, a large amountof iodide salts, and thioether compounds, metho-ionic compounds, andnitrogen-containing heterocyclic compounds, having a sulfide group, asdescribed in JP-A-4-365037, pages 11 to 21, and JP-A-5-66540, pages 1088to 1092. Among these, use of thiosulfates is usual, and ammoniumthiosulfate is most widely used. A combination of thiosulfates withthiocyanates, thioether compounds, thiourea, or metho-ionic compounds,is also preferable.

Preferable preservatives for the fixing solution and the bleach-fixsolution are sulfites, bisulfites, carbonylbisulfite adducts, andsulfinic acid compounds described in European Patent No. 294 769(A). Inthe fixing solution, the bleaching solution, and the bleach-fixsolution, to stabilize the solutions, it is preferable to add any ofvarious aminopolycarboxylic acids, organic phosphonic acids (e.g.1-hydroxyethylidene-1,1-diphosphonic acid,N,N,N′,N′-ethylenediaminetetraphosphonic acid, and2-phosphonobutane-1,2,4-ticarboxylic acid) and sodium stannate.

In the fixing solution and the bleach-fix solution, further, forexample, any of various fluorescent whitening agents, antifoamingagents, surface-active agents, polyvinylpyrolidones, and methanol can becontained.

The processing temperature of the desilvering step is 20 to 50° C., andpreferably 30 to 45° C. The processing time is 5 sec to 2 min, andpreferably 5 sec to 1 min. Although a small replenishing rate ispreferable, the replenishing rate is 15 to 600 ml, preferably 25 to 200ml, and more preferably 35 to 100 ml, per m² of the photographicmaterial. The processing is also preferably carried out withoutreplenishment in such a way that the evaporated amount is supplementedwith water.

The photographic material of the present invention is generally passedthrough a washing (rinsing) step after the desilvering process. If astabilizing process is carried out, the washing step can be omitted. Insuch a stabilizing process, processes described in JP-A-57-8543,58-14834, and 60-220345, and all known processes described inJP-A-58-127926, 58-137837, and 58-140741, can be used. Awashing-stabilizing process, in which a stabilizing bath containing adye stabilizer and a surface-active agent typically used for theprocessing of color photographic materials for photographing is used asa final bath, can be carried out.

In the washing liquid and stabilizing solution, use can be made of awater softener, such as sulfites, inorganic phosphoric acids,polyaminocarboxylic acids, and organic aminophosphoric acids; a metalsalt, such as Mg salts, Al salts, and Bi salts; a surface-active agent,a hardener, a pH buffer, a fluorescent whitening agent, and asilver-salt-forming agent, such as nitrogen-containing heterocycliccompounds.

Example dye-stabilizing agents of the stabilizing solution include, forexample, aldehydes, such as formaldehyde and glutaraldehyde; N-methylolcompounds, hexamethylenetetramine, or aldehyde sulfite adducts.

The pH of the washing liquid and the stabilizing solution is 4 to 9, andpreferably 5 to 8. The processing temperature is 15 to 45° C., andpreferably 25 to 40° C. The processing time is 5 sec to 2 min, andpreferably 5 sec to 40 sec.

The overflow liquid associated with the replenishment of the abovewashing liquid and/or the stabilizing solution, can be reused in otherprocesses, such as the desilvering process.

The amount of the washing liquid and/or the stabilizing solution can beset in a wide range depending on various conditions, and thereplenishing rate is preferably 15 to 360 ml, and more preferably 25 to120 ml, per m² of the photographic material. To reduce the replenishingrate, it is preferable to use multiple tanks and a multi-stagecountercurrent system. In particular, it is preferable to use 2 to 5tanks. In order to prevent the propagation of bacteria and adhesionstain of suspended matter on the photographic material that will resultfrom reduction in the amount of these solutions, use can be made ofbactericides, such as sodium chlorinated isocynurate, cyapentazoles, andisothiazolone compounds described in JP-A-57-8542; other benzotriazoles;and bactericides described by Hiroshi Horiguchi in “Bokin-bobaizai noKagaku” (1986, Sankyo-shuppan); in “Biseibutsu no Mekkin, Sakkin, BobaiGijutsu,” edited by Eisei Bobai-gakkai (1982, Kogyo Gijutsu-kai); and in“Bokin Babai-zai Jiten,” edited by Nihon Bokin Bobai-gakkai (1986).Further, a method of reducing Mg and Ca ions, as described inJP-A-62-288838, is particularly preferably used.

In the present invention, in order to save water, water can be used thathas been obtained by treating the overflow liquid or the in-tank liquidusing a reverse osmosis membrane. For example, the treatment by reverseosmosis is preferably carried out for water from the second tank, or themore latter tank of the multi-stage countercurrent washing processand/or the stabilizing process. Specifically, in the case of a two-tanksystem, the water in the second tank is treated by a reverse osmosismembrane, and in the case of a four-tank system, the water in the thirdtank and the fourth tank is treated by a reverse osmosis membrane, andthen the passed water is returned to the first tank (the tank from whichwater for the reverse osmosis treatment has been taken) or is brought toa washing tank and/or a stabilizing tank situated downstream. It is alsoone mode that the concentrated liquid is returned to a tank situatedupstream of that particular tank and further to the desilvering bath.

As the material of the reverse osmosis membrane, for example, celluloseacetates, crosslinked polyamides, polyethers, polysulfons, polyacrylicacids, and polyvinylene carbonates can be used. The pressure of thepumped liquid used for these membranes is preferably 2 to 10 kg/cm² andparticularly preferably 3 to 7 kg/cm².

In the present invention, preferably the stirring is intensified as muchas possible. To intensify the stirring, specifically a method wherein ajet stream of a processing liquid is caused to impinge on the emulsionsurface of a photographic material, as described in JP-A-62-183460 and62-183461; a method wherein a rotating means is used to increase thestirring effect, as described in JP-A-62-183461; a method wherein aphotographic material is moved, with the emulsion surface of thematerial being in contact with a wiper blade provided in a liquid, sothat a turbulent flow may occur near the emulsion surface, to improvethe stirring effect; and a method wherein the total amount of aprocessing solution to be circulated is increased, can be mentioned.These means of improving the stirring are useful in any of thedeveloping solution, the bleaching solution, the bleach-fix solution,the stabilizing solution, and the washing liquid. These methods areeffective in that the effective constituents in the solution aresupplied to the photographic material and the diffusion of unnecessarycomponents in the photographic material is promoted.

In the present invention, any state of a liquid opening rate [contactarea of air (cm²)/liquid volume (cm³)] of any of the baths can exhibitexcellent performance, but in view of the stability of the liquidcomponents, preferably the liquid opening rate is 0 to 1.0 cm⁻¹. In thecontinuous processing, from a practical point of view, the liquidopening rate is preferably 0.001 to 0.05 cm⁻¹, and more preferably 0.002to 0.03 cm⁻¹.

The automatic processor used for the photographic material of thepresent invention is preferably provided with a means of transporting aphotographic material, as described in JP-A-60-191257, 60-191258, and60-191259. Such a transporting means can reduce remarkably the carry-inof the processing solution from a preceding bath to a succeeding bath.Therefore, it is high in the effect of preventing the performance of aprocessing solution from being deteriorated. Such an effect is effectivein shortening the processing time of each process and in reducing theprocess replenishing rate. To shorten the processing time, it ispreferable to shorten the crossover time (the aerial time), and a methodwherein a photographic material is transported between processes througha blade having a screening effect, as described, for example, inJP-A-4-86659, FIG. 4, 5, or 6, and JP-A-5-66540, FIGS. 4 or 5, ispreferable.

Further, if each of the processing solutions in the continuous processis concentrated due to evaporated, preferably water is added tocompensate for the evaporation.

The processing time in each process according to the present inventionmeans the time required from the start of the processing of thephotographic material at any process, to the start of the processing inthe next process. The actual processing time in an automatic processoris determined generally by the linear speed and the volume of theprocessing bath, and in the present invention, as the linear speed, 500to 4,000 mm/min can be mentioned as a guide. Particularly in the case ofa small-sized processor, 500 to 2,500 mm/min is preferable.

The processing time in the whole processing steps, that is, theprocessing time from the activator development process to the dryingprocess, is preferably 360 sec or below, more preferably 120 sec orbelow, and particularly preferably 90 to 30 sec. Herein the processingtime means the period from the dipping of the photographic material intothe activator solution, till the emergence from the drying part of theprocessor.

The color-developing agent and coupler used in the present invention maybe used for a light-sensitive element for color diffusion transfermethod in which it is developed using a treating solution at around roomtemperature and for a thermal developing light-sensitive element whichis developed by heating.

The silver halide which may be used for the above light-sensitiveelement may be any one of silver chloride, silver bromide, silverchlorobromide, silver chloroiodide and silver chloroiodobromide.

Specifically, any one of silver halide emulsions described in U.S. Pat.No. 4,500,626, 50th column, Journal of Research & Disclosure, the Juneissue, pp9-10 (1978) (RD17029), JP-A-61-107240, JP-A-62-85241 andJP-A-62-87957 may be used.

The silver halide emulsion used in the present invention may be either asurface latent image type in which a latent image is primarily formed onthe surface of a grain or an internal latent image type in which alatent image is formed inside of a grain. The silver halide emulsionused in the present invention may also be a core/shell emulsion in whichthe inside and surface of a grain are formed of different layers. In thepresent invention, a direct reverse emulsion in which an internal latentimage type emulsion is combined with a core-forming agent and/or a lightcablace may be used.

Although a silver halide emulsion may be used just withoutafter-ripening, it is usually used after it is chemically sensitized. Inthe case of normal light-sensitive material emulsions, a well-knownsulfur sensitization method, reduction sensitization method and noblemetal sensitization method may be used either singly or in combination.These chemical sensitizations may be carried out in the presence of anitrogen-containing heterocyclic compound (JP-A-58-126526 andJP-A-58-215644). Usually the coating amount of the light-sensitivesilver halide used in the present invention is 1 mg to 10 g/m², in termsof silver.

Also, the color-developing agent and coupler of the present inventionmay be used together with known dye-donating compounds including dyedeveloping agents described later and compounds releasing a diffusibledye by a redox reaction in the same photographic element. For instance,a method may be used in which yellow and cyan images are formed by thecolor-developing agent represented by formula (1) or (2) and coupler ofthe present invention and a magenta image is formed by other dyeimage-forming compounds. Further, for instance, a method may be used inwhich a magenta image is formed by the color-developing agentrepresented by formula (3) and coupler represented by formula (4)defined in the present invention and yellow and cyan images are formedby other dye image-forming compounds.

As the dye image-forming compound which may be used together in thepresent invention, first, combinations of known developers and couplerswhich can react therewith may be typified. This system using a coupleris to form a dye by reacting an oxidized product of developer, which isproduced by a redox reaction between a silver salt and the developingagent, with the coupler and is described in abundant literature. Thiscoupler may be either a four-equivalent coupler or a two-equivalentcoupler. It is also preferable to use a two-equivalent coupler which hasa diffusion resistant group in an elimination group and produces adiffusible dye by the reaction with the oxidized product of thedeveloper. Specific examples of the developing agent and the coupler aredescribed in detail, for example, in “Theory of The PhotographicProcess” (4th Ed., edited by T. H. James), pages 291 to 334 and 354 to361, and in JP-A-58-12353, 58-149046, 58-149047, 59-111148, 59-124399,59-174835, 59-231539, 6-231540, 60-2950, 60-2951, 60-14242, 60-23474,and 60-66249.

In addition, as dye-image forming compounds, for example, dye silvercompounds formed by combining an organic silver salt with a dye can bementioned. Examples of dye silver compound is described in, for example,Research Disclosure, May, 1978, pages 54 to 58 (RD-16966).

Further, azo dyes used in the heat-developable silver dye bleach processcan be mentioned as an example of dye-image forming compound. Specificexamples of azo dyes and bleaching methods are described in, forexample, U.S. Pat. No. 4,235,957 and Research Disclosure, April, 1976,pages 30 to 32 (RD-14433). In addition, leuco dyes described in, forexample, U.S. Pat. No. 3,985,565 and U.S. Pat, No. 4,022,617 can bementioned as an example.

Further, as an example of other dye-image forming compound, compoundshaving a function of releasing or diffusing a diffusion dye imagewisecan be mentioned.

The compounds of this type can be represented by the following formula[LI]:

(Dye-X)_(n)−Y  [LI]

Dye represents a dye group, a dye group whose wavelength is temporarilyshortened, or a dye precursor group, X represents a mere single bond ora linking group, Y represents a group which has such a property thatproduces a difference in the diffusibility of the compound representedby (Dye-X)_(n)−Y correspondingly or inversely-correspondingly to thelight-sensitive silver salt having a latent image imagewise, or thatreleases Dye, to produce a difference in the diffusibility between Dyereleased and (Dye-X)_(n)−Y. n is 1 or 2, and when n is 2, a plurality ofDye-Xs may be the same or different.

As specific examples of the dye-donating material represented by theformula [LI], dye developers in which a hydroquinone type developer iscombined with a dye component are described in U.S. Pat. No. 3,134,764,U.S. Pat. No. 3,362,819, U.S. Pat. No. 3,597,200, U.S. Pat. No.3,544,545 and U.S. Pat. No. 3,482,972. Also, materials releasing adiffusible dye by an intermolecular nucleophilic substitution reactionand by an intermolecular rollback reaction of isoxazolone ring aredescribed in JP-A-51-63618 and JP-A-49-111628 respectively. In all ofthese methods, a diffusible dye is released or diffused in undevelopedparts, but neither released nor diffused in developed parts.

A further method has been devised in which a dye-releasing compound ismade to be an oxidized product type incapable of releasing a dye and tocoexist together with a reducing agent or its precursor and after beingdeveloped, the dye-releasing compound is reduced by a reducing agentleft non-oxidized to thereby release a diffusible dye. Specific examplesof the dye image-forming compound used in this method are described inJP-A-53-110,827, JP-A-54-130,927, JP-A-56-164,342 and JP-A-53-35,533.

As materials releasing a dye in developed parts, materials releasing adiffusible dye by a reaction between a coupler having a diffusible dyein an elimination group and an oxidized product of a developer aredescribed in U.K. Patent No. 1,330,524, JP-B-48-39,165 and U.S. Pat. No.3,443,940.

In the system using these color-developers, image contaminations withoxidation-decomposed products of the developer cause a serious problem.A dye-releasing compound which needs no developing agent and itself hasreducibility has been devised to solve the problem. Typical examples ofthe dye-releasing compound include dye image-forming compounds describedin U.S. Pat. No. 3,928,312, U.S. Pat. No. 4,053,312, U.S. Pat. No.4,055,428 and U.S. Pat. No. 4,336,322, JP-A-59-65839, JP-A-59-69839,JP-A-51-104,343, Journal of Research & Disclosure No. 17465, U.S. Pat.No. 3,725,062, U.S. Pat. No. 3,728,113 and U.S. Pat. No. 3,443,939,JP-A-58-116537, JP-A-57-179840 and U.S. Pat. No. 4,500,626.

In the system forming an image by diffusion transfer of a dye by usingthe light-sensitive material of the present invention, thelight-sensitive materials are generally divided into two types: one typein which a light-sensitive element and an image-receiving element(dye-fixing element) are formed separately by application on twosupports (these may be referred to a light-sensitive material anddye-fixing material, respectively) and another type in which the bothare formed by application on the same support.

The mutual relations of the light-sensitive element to the dye-fixingelement, to the supports and to a white reflecting layer which aredescribed in the specification of JP-A-61-147244, pp58-59 and U.S Pat.No. 4,500,626, 57th column may be applied to the light-sensitivematerial of the present invention.

A typical type of film unit in which a light-sensitive element and animage receiving element are formed on the same support is one in whichthe image-receiving element and the light-sensitive element arelaminated on one transparent support and which eliminates the necessityof peeling the light-sensitive element from the image-receiving elementafter a transferred image is completed. To state in more detail, theimage-receiving element comprises at least one mordant layer (alsocalled an image-receiving layer or a dye-fixing layer). Also, thelight-sensitive element, in preferred embodiments, comprises acombination of a blue-sensitive emulsion layer, green-sensitive emulsionlayer and red-sensitive emulsion layer, a combination of agreen-sensitive emulsion layer, red-sensitive emulsion layer andinfrared-light-sensitive emulsion layer or a combination of ablue-sensitive emulsion layer, red-sensitive emulsion layer andinfrared-light-sensitive emulsion layer. Moreover, a yellow dyeimage-forming compound (a dye image-forming compound containing thecolor-developing agent and coupler of the present invention), a magentadye image-forming compound (a dye image-forming compound containing thecolor-developing agent and coupler of the present invention) and a cyandye image-forming compound (a dye image-forming compound containing thecolor-developing agent and coupler of the present invention) arerespectively combined with the above emulsion layers. Thus, theimage-forming system of the present invention is structured (Here, the“infrared-light-sensitive emulsion layer” means an emulsion layerpossessing sensitivity to light of 700 nm or more and especially 740 nmor more). Each of these light-sensitive emulsion layers may be dividedinto two or more layers as required. in addition, a white reflectinglayer containing a solid dye, e.g., titanium oxide, is formed betweenthe mordant layer and the light-sensitive layer or the dye image-formingcompound (the dye image-forming compound containing the color-developingagent and coupler of the present invention) so as to observe thetransferred image through the transparent support. A shading layer maybe further formed between the white reflecting layer and thelight-sensitive layer so as to complete developing treatment in lightfields. Also, as desired, a peelable layer may be formed at a properposition to peel all or a part of the light-sensitive element from theimage-receiving element (embodiments like this are described inJP-A-56-67840 and C.A. Patent No. 674,082).

In other types which do not need peeling, the light-sensitive element isformed by application on one transparent support, a white reflectinglayer is formed by application on the light-sensitive element and animage-receiving layer is further laminated on the white reflectinglayer. The type in which an image-receiving element, a white reflectinglayer, a peelable layer and a light-sensitive element are laminated onthe same support and the light-sensitive element is intentionally peeledfrom the image-receiving element is described in U.S. Pat. No.3,730,718. On the other hand, the typical types in which thelight-sensitive element and the image-receiving element are separatelyformed by application on two supports are loosely divided into twocategories: one category is a peelable type and another category is apeeling-needless type. To mention these types in detail, in a preferredembodiment of the peelable film unit, a light-reflecting layer isprovided on the backface of a support and at least one image-receivinglayer is formed by application on the surface of the support. Also, thelight-sensitive element is formed by application on a support providedwith a shading layer. This embodiment is devised such that the surfaceof the applied light-sensitive layer does not face the surface of theapplied mordant layer until the exposure is finished, but the surface ofthe applied light-sensitive layer is overturned so that it faces thesurface of the applied mordant layer after the exposure was finished(for instance, during developing). The light-sensitive element is peeledfrom the image-receiving element immediately after the transferred imageis completed.

In a preferred embodiment of the peeling-needless film unit, at leastone mordant layer is formed on a transparent support and alight-sensitive element is formed by application on a support providedwith a transparent or shading layer and the surface of the appliedlight-sensitive layer and the surface of the applied mordant layer arefacing and are overlapped on each other.

The aforementioned modes may be applied to both of a system ofdevelopment using an alkaline solution which is developed (expanded) ina light-sensitive material, and a heat development system. In,particularly, the former system, a container (treating element) whichcontains the process alkaline solution and can be burst may be combined.In, among these systems, the peeling-needless film unit in which animage-receiving element and a light-sensitive element are laminated onone support, the treating unit is preferably disposed between thelight-sensitive element and a cover sheet which is overlapped on thelight-sensitive element. Also, in the type in which a light-sensitiveelement and an image-receiving element are separately formed byapplication on two supports, the treating element are preferablydisposed between the light-sensitive element and the image-receivingelement during the developing time at the latest. Preferably thetreating element contains a shading agent (e.g., carbon black and dyeswhich are changed in color depending upon pH) and/or a white pigment(titanium oxide) according to the type of film unit. In a film unit ofthe type which develops using a process alkali solution, preferably aneutralization-timing mechanism consisting of a combination of aneutralization layer and a neutralization timing layer is incorporatedinto the cover sheet, the image-receiving element or the light-sensitiveelement.

As the mordant agent used in the aforementioned image-receiving elementor the dye-fixing element explained later, a polymer mordant agent ispreferable. Here, the polymer mordant agents are, for example, polymerscontaining a tertiary amino group, polymers containing anitrogen-containing heterocyclic portion and polymers containing aquaternary cationic group.

Specific examples of these polymer mordant agents are described inJP-A-61-147244, pp98-100 and U.S. Pat. No. 4,500,626, 57th-60th columns.

When the present invention is applied to a heat-developablelight-sensitive material, the silver halide may be used together with anorganic metal salt as an oxidizing agent. In this case, it is necessarythat the light-sensitive silver halide and the organic metal salt are incontact with each other or close to each other.

Among these organic metal salts, organic silver salts are usedparticularly preferably.

Examples of organic compounds which may be used to produce the aboveoxidized product of organic silver salt include compounds described inJP-A-61-107240, pp37-39 and U.S. Pat. No. 4,500,626, 52th-53th columns.Silver salts of carboxylic acid having an alkinyl group, such as silverphenylpropiolate, described in JP-A-60-113235 and silver acetylidedescribed in JP-A-61-249044 are also useful. organic silver salts may beused in combinations of two or more.

Among such organic metal salts, organic silver salt is particularlypreferably used.

As the organic compound that can be used to form the above organicsilver salt oxidizing agent, compounds described in JP-A-61-107240,columns 37 to 39, and those described in U.S. Pat. No. 4,500,626,columns 52 to 53, can be mentioned. Further, a silver salt of acarboxylic acid having an alkinyl group, such as silverphenylpropiolate, described in JP-A-60-113235, and silver acetylidedescribed in JP-A-61-249044 are also useful. Organic silver salts may beused in combination of two or more.

The above organosilver salts may be used additionally in an amount ofgenerally 0.01 to 10 mol, and preferably 0.01 to 1 mol, per mol of thelight-sensitive silver halide. Suitably the total coating amount of thelight-sensitive silver halide plus the organosilver salt is generally 50mg to 10 g/m², in terms of silver.

Hydrophobic additives among the aforementioned additives may beintroduced into the layers of the light-sensitive material according toa known method as described in U.S. Pat. No. 2,322,027. In this case,high-boiling point organic solvent as described in JP-A-59-83154,JP-A-59-178451, JP-A-59-178452, JP-A-59-178453, JP-A-59-178454,JP-A-59-178455 and JP-A-59-178457 may be used, as required, togetherwith a low-boiling point organic solvent having a boiling point as lowas 50° C. to 160° C.

Also, a dispersion method using a polymer as described in JP-B-51-39853and JP-A-51-59943 may be used.

In the case of compounds which are substantially insoluble in water,they may be made into fine grains, which are dispersed in a binderinstead of using the aforementioned methods.

When a hydrophobic material is dispersed in a hydrophilic colloid,various surfactants may be used. For example, those described assurfactants in JP-A-59-157636, pp37-38 may be used.

In the present invention, reducing materials may be desirably used inthe light-sensitive element. The reducing materials generally include,other than those known as reducing agents, the aforementioned dyeimage-forming compound containing the color-developing agent used in thepresent invention. The reducing materials also include a reducing agentprecursor which itself has no reducibility but develops reducibility bythe effect of a nucleophilic agent or heat during a developing stage.

Examples of the reducing agent which can be utilized in the presentinvention include those described in U.S. Pat. No. 4,500,626, 49th-50thcolumns, U.S. Pat. No. 4,483,914, 30th-31th columns, JP-A-60-140335,pp17-18, JP-A-60-128438, JP-A-60-128436, JP-A-60-128439 andJP-A-60-128437. Reducing agent precursors described in JP-A-56-138736,JP-A-57-40245 and U.S. Pat. No. 4,330,617 may also be utilized.

Moreover, combinations of various reducing agents as described in U.S.Pat. No. 3,039,869 may be used.

In the present invention, the amount of the reducing agent to be addedis 0.01 to 20 mols and particularly preferably 0.1 to 10 mols based on 1mol of silver.

In the present invention, compounds which improve developing activityand the stability of an image may be used in the light-sensitiveelement. Specific compounds which are preferably used are described inU.S. Pat. No. 4,500,626, 51th-52th columns.

In the present invention, various fog-preventive agent and photographicstabilizers may be used. Examples of these agents which may be used inthe present invention include azoles and azaindenes described in Journalof Research & Disclosure, the December issue, pp24-25 (1978),nitrogen-containing carboxylic acids and phosphoric acids described inJP-A-59-168442, mercapto compounds and their metal salts described inJP-A-59-111636 and acetylene compounds described in JP-A-62-87957.

In the present invention, the light-sensitive element may include animage color-adjusting agent as required. Specific examples of effectivecolor-adjusting agents include compounds described in JP-A-61-147244,pp92-93.

The light-sensitive element used in the present invention may comprise,as required, various additives which are known as materials used for aheat developing light-sensitive element and layers other than thelight-sensitive layer such as a protective layer, intermediate layer,antistatic layer, antihalation layer, peelable layer which makes peelingfrom a dye-fixing element easy and a matte layer. These variousadditives include plasticizers, matte agents, vividness-improving dyes,antihalation dyes, surfactants, fluorescent brighteners, antislipagents, antioxidized products, color fading preventive agents anddiffusible dye trap agent, which are all described in Journal ofResearch & Disclosure, the June issue, pp9-15 (1978) and JP-A-61-88256.

Especially the protective layer is usually made to contain organic andinorganic matte agents to prevent adhesion. This protective layer mayalso include a mordant agent and a UV-ray absorber. The protective layerand the intermediate layer may be respectively structured of two or morelayers.

Also, the intermediate layer may include a reducing agent, a UV-rayabsorber and a white pigment, e.g., titanium dioxide to preventcolor-fading and color mixing. The white pigment may be added not onlyto the intermediate layer but also to the emulsion layer to improve thesensitivity.

The dye-fixing element may be provided with auxiliary layers such as aprotective layer, peelable layer and curling preventive layer asrequired. Particularly it is useful to provide the protective layer. Oneor more of the aforementioned layers may include hydrophilic heatsolvents, plasticizers, color-fading preventive agents, UV-rayabsorbers, anti-slip agents, matte agents, antioxidized products,disperse vinyl compounds for increasing dimentional stability,surfactants, luminescent whiteners and the like. Further, particularly,in the system wherein the heat development and the transfer of the dyeare carried out simultaneously in the presence of a small amount ofwater, a base and/or a base precursor is preferably contained in thedye-fixing element, with a view to increasing the preservability of thelight-sensitive element. Specific examples of these additives aredescribed in JP-A-61-88256, pages 101 to 120.

In the light-sensitive element and/or the dye-fixing element accordingto the present invention, an image-forming promoter may be used. Theimage-forming promoter has an ability to promote a redox reactionbetween a silver salt oxidizing agent and a reducing agent, an abilityto promote reactions to produce a dye from the dye image-formingcompound containing the color-developing agent and coupler of thepresent invention, to decompose the dye and to release a diffusible dyefrom the dye image-forming compound and an ability to promote thetransfer of the dye from the structural layer of the light-sensitiveelement to the dye-fixing layer. From the physicochemical abilities, theimage-forming promoters are classified into bases or base precursors,nucleophilic compounds, high boiling point organic solvents (oil), heatsolvents, surfactants, compounds which interact with silver or silverions and the like. It is to be noted that these material groups usuallyhave duplex abilities and possess some of the above promoting effects ingeneral. The details of these materials are described in JP-A-61-93451,pp67-71.

There are various methods for the production of a base. Compounds usedin these methods are all useful as a base precursor. There are, forexample, a method described in E.P. Patent No. 0210660A2 in which a baseis generated by mixing a metal compound (e.g., metal salts), which issparingly soluble in water, with a compound (a complex-forming compoundor complexing agent) which can react with metal ions constituting themetal compound, which is sparingly soluble in water, to form a complexand a method described in JP-A-61-232451 in which a base is generated byelectrolysis.

Especially, the former method is effective. Given as examples of themetal salt which is sparingly soluble in water are carbonates,hydroxides or oxides of zinc, aluminum, calcium or barium. Thecomplex-forming compounds are explained in detail, for example, in“Critical Stability Constants” written jointly by “A. E. Martell, R. M.Smith, Vol No. 4 and Vol. No. 5, Plenum Press. Specific examples includesalts of aminocarboxylic acids, iminodiacetic acids, pyridinecarboxylicacids, aminophosphoric acids, carboxylic acids (mono-, di-, tri-,tetra-carboxylic acids and compounds having each of substituents, e.g.,a phosphono, hydroxy, oxo, ester, amide, alkoxy, mercapto, alkylthio orphosphino group), hydroxam acids, polyacrylates or polyphosphoric acidsand alkali metals, guanidines, amidines or quaternary ammonium salts.

It is advantageous to add these metal compound which is sparing solublein water and complex-forming compound to each of the light-sensitiveelement and dye-fixing element.

In the light-sensitive element and/or the dye-fixing element for use inthe present invention, in order to obtain a constant image all the time,against fluctuation of the processing temperature and the processingtime at the time of development, various development-stopping agents canbe used.

Herein, the term “a development-stopping agent” means a compound thatneutralizes bases quickly or reacts quickly with bases after properdevelopment, to lower the base concentration in the film, to stop thedevelopment; or a compound that interacts with silver and silver salts,to inhibit the development. Specific examples include acid precursorsthat release an acid when heated, electrophilic compounds that undergo asubstitution reaction with coexisting bases when heated,nitrogen-containing heterocyclic compounds, mercapto compounds, andtheir precursors (for example, compounds described in JP-A-60-108837,JP-A-60-192939, JP-A-60-230133, and JP-A-60-230134).

Also, compounds which release a mercapto compound by heating are alsouseful. These compounds are described in, for example, JP-A-61-67851,JP-A-61-147244, JP-A-61-124941, JP-A-61-185743, JP-A-61-182039,JP-A-61-185744, JP-A-61-184539,. JP-A-61-188540 and JP-A-61-53632.

As the binder of light-receiving element and/or dye-fixing element ofthe present invention, a hydrophilic binder is preferably used.Typically, the hydrophilic binder is a transparent or semitranparenthydrophilic binder. Specifically, examples include natural compoundssuch as proteins including gelatin, gelatin derivatives and the like, orpolysaccharides including cellulose derivatives, starches, gum-arabic,dextrans, and the like; and synthetic polymer compounds such as watersoluble polyvinyl compounds including polyvinyl pyrrolidones, andacrylamide polymers. A disperse vinyl compound which is used in the formof a latex and increase the dimentional stability of photographicmaterials may also be used. These binders may be used either singly orin combinations.

It is proper that the amount of the binder to be applied in the presentinvention is 20 g or less, preferably 10 g or less and more preferably 7g or less per 1 m².

A proper ratio of a high-boiling point organic solvent dispersed in thebinder together with hydrophobic compounds such as the color-developingagent and coupler of the present invention to the binder is as follows:the amount of the solvent is 1 cc or less, preferably 0.5 cc or less andmore preferably 0.3 cc or less based on 1 g of the binder.

The light-sensitive element and/or the structural layer (e.g., aphotographic emulsion layer and a dye-fixing layer) of the dye-fixingelement in the present invention may contain an inorganic or organichardener.

Specific examples of the hardener include those described in thespecification of JP-A-61-147244, pp94-95 and in the specification ofJP-A-59-157636, pp38. These compounds may be used either singly or incombination.

To accelerate the dye transfer, a system can be adopted wherein ahydrophilic heat solvent that is solid at normal temperatures and meltsat a higher temperature is built in the light-sensitive element and/orthe dye-fixing element. The heat solvent can be is built in any oflight-sensitive element and dye-fixing element, and it may be built inboth elements. Further, the layer wherein the hydrophilic heat solventis built in may be any of the emulsion layer, the intermediate layer,the protective layer, and the dye-fixing layer, but preferably it is thedye-fixing layer and/or the layer adjacent thereto. Examples of thehydrophilic heat solvent include ureas, pyridines, amides, sulfonamides,imides, alcohols, oximes, and other heterocyclic compounds. Further, toaccelerate the dye transfer, high-boiling organic solvent can becontained in a light-sensitive element and/or image-receiving element.

The support used for the light-sensitive element and/or the dye-fixingelement can stand against treating temperature. As a usual support,glass, paper, polymer films, metals or similar materials may be used andalso those described as supports in the specification of JP-A-61-147244,pp95-96 may be used.

The light-sensitive element and/or the dye-fixing element may be a typehaving a conductive exothermic body layer to be used as a heating meansfor heating development or the transfer of a dye.

A transparent or opaque exothermic element in this case may be made as aresistive exothermic body by making use of conventionally well-knowntechniques. As the method of producing the resistive exothermic body,there are a method which makes use of a thin film of an inorganicmaterial exhibiting semiconductivity and a method which makes use of anorganic thin film in which electroconductive fine grains are dispersedin a binder. As materials used in these methods, compounds described inthe specification of JP-A-61-29835 may be used.

In the present invention, to apply a heat developing light-sensitivelayer, protective layer, intermediate layer, undercoat layer, backlayer, dye-fixing layer and other layers, a method described in U.S.Pat. No. 4,500,626, 55th-56th columns can be used.

As a light source for image exposure used to record an image in thelight-sensitive element, radiation rays including visible light may beused. In general, light sources used in usual color printing, forinstance, a tungsten lamp, mercury lamp, halogen lamps such as an iodinelamp, xenon lamp, laser light source, CRT light source or light emittingdiode (LED), which are all described in JP-A-61-147244, pp100 and U.S.Pat. No. 4,500,626, 56th column, may be used.

In the image-forming method involving a heating step to which thepresent invention is applied, for example, a heat developing step and adye-transfer step are carried out either separately or simultaneously.Also, both steps may be successive in the meaning of the fact that atransfer operation is carried out in succession to a developingoperation in one step.

For instance, there are (1) a method in which an image is formed on thelight-sensitive element by exposure, followed by heating, thereafter adye-fixing element is overlapped on the light-sensitive element and, asrequired, heated to transfer a movable dye to the dye-fixing element and(2) a method in which an image is formed on the light-sensitive elementby exposure and a dye-fixing element is overlapped on thelight-sensitive element, followed by heating. The aforementioned methods(1) and (2) may be applied either in substantially the absence of wateror in the presence of minute water.

The heating temperature in the heat developing step, although thedevelopment can be made at about 50 to 250° C., is preferably 70° C. to180° C. and particularly preferably 75° C. to 150° C. In the case ofheating in the presence of minute water, the upper limit of the heatingtemperature is below the boiling temperature. When the transfer step isperformed after the heat developing step is finished, the heatingtemperature in the transfer step, though the transfer can be made in atemperature range between the temperature in the heat developing stepand room temperature, is more preferably above 50° C. and lower than thetemperature in the heat developing step by 10° C.

In a preferred image-forming method according to the present invention,an image is exposed or heating is performed in the presence of minutewater and a base and/or a base precursor when an image is exposed and adiffusible dye generated in the parts corresponding or reverselycorresponding to a silver image at the same time of developing istransferred to the dye-fixing layer. This method ensures that theproduction and releasing reactions of the diffusible dye run veryquickly and hence the diffusible dye is transferred to the dye-fixinglayer rapidly thereby to obtain a high density color image in a shortperiod of time.

The amount of water to be used in this embodiment is as small as 0.1times and preferably more than 0.1 times the weight of the total appliedfilm of the light-sensitive element and dye-fixing layer and less thanthe amount (specifically, less than the amount calculated by subtractingthe weight of the total applied film from the weight of the solventcorresponding to the maximum swelled volume of the total applied film)of the solvent corresponding to the maximum swelled volume of the totalapplied film.

The condition of the film during swelling is unstable and local bleedingis likely caused depending upon the condition. In order to evade thisphenomenon, the amount of water is preferably smaller than the amountcorresponding to the volume of the total applied film of thelight-sensitive element and dye-fixing element when the film reaches amaximum swelling. Concretely, the amount of water is in a range between1 and 50 g, preferably 2 and 35 g and more preferably 3 and 25 g.

A base and/or base precursor used in this embodiment may be incorporatedinto the light-sensitive element and the dye-fixing element. The baseand/or base precursor may also be supplied after it is dissolved inwater.

In the above embodiment, it is preferable that the image-formingreaction system be made to contain a metal compound (e.g., a basic metalcompound which is sparing soluble in water), which is sparing soluble inwater, as a base precursor and a compound (a complexing agent) which canreact with a metal ion constituting the metal compound, which is sparingsoluble in water, by using water as a medium to form a complex and analkali be generated by the reaction of both compounds during heating toraise the pH of the system. Here, the image reaction system means theregion where an image-forming reaction is caused. Given as specificexample of the region are layers belonging to both of thelight-sensitive element and dye-fixing element. In the case where two ormore layers are present, the reaction system may be included in any ofthese layers.

It is necessary to add the metal compound which is sparing soluble inwater and the complex-forming compound to at least separate layers toprevent the both from reacting with each other by the time of developingtreatment. For example, in a so-called monosheet material in which thelight-sensitive element and the dye-fixing element are formed in thesame support, it is desirable that the layers to which the both areadded separately and one or more layers are interposed between theseseparate layers. In a more preferred embodiment, the metal compoundwhich is sparingly soluble in water and the complex-forming compound arerespectively contained in each layer formed on separate supports. Forexample, it is desirable that the metal compound which is sparinglysoluble in water be contained in the light-sensitive element and thecomplex-forming compound be contained in the dye-fixing element having asupport different from that of the light-sensitive element. Thecomplex-forming compound may be supplied after it is dissolved in waterallowed to coexist. Preferably the metal compound which is sparinglysoluble in water is contained in the form of a fine grain dispersionprepared according to the methods described in, for example,JP-A-56-17480 and JP-A-53-102733. Preferably the average grain size ofthe fine grain dispersion is 50μm or less and particularly 5 μm or less.The metal compound which is sparingly soluble in water may be added toany one of the light-sensitive layer, intermediate layer and protectivelayer of the light-sensitive element and may be added separately to twoor more layers.

When the metal compound which is sparingly soluble in water or thecomplex-forming compound is to. be contained in a layer on a support,the amount of the compound depends on the type of compound, the grainsize of the metal compound which is insoluble in water and the rate ofreaction for forming a complex. The metal compound or thecomplex-forming compound is used preferably in an amount of 50% byweight or less and more preferably in an amount ranging from 0.01% byweight to 40% by weight. When the complex-forming compound is suppliedafter it is dissolved in water, its concentration is in a rangepreferably from 0.005 mols to 5 mols and particularly from 0.05 mols to2 mols per 1 liter of the solution. In the present invention, thecontent of the complex-forming compound in the reaction system ispreferably 1/100 times to 100 times and particularly preferably 1/10times to 20 times the content of the compound, which is sparinglysoluble in water, in terms of molar ratio.

A method of supplying water to the light-sensitive layer or thedye-fixing layer includes, for example, one described in JP-A-61-147244,pp101, line 9 to pp102, line 4.

As heating means in the developing step and/or transfer step, there aremeans described in JP-A-61-147244, pp102, line 14 to pp103, line 11, forexample, a heating plate, iron and heat roller. A method may be adoptedin which layers of conductive materials such as graphite, carbon blackand metals are overlapped on the light-sensitive element and/ordye-fixing element and current is allowed to flow through the conductivelayer to heat directly.

As pressure conditions and a method of applying pressure when thelight-sensitive element and the dye-fixing element are overlapped oneach other and stuck to each other, a method described inJP-A-61-147244, pp103 to 104 may be used.

To process the photographic elements for use in the present invention,any of various heat development apparatuses can be used. For example,apparatuses described, for example, in JP-A-59-75247, JP-A-59-177547,JP-A-59-181353, and JP-A-60-18951, unexamined published Japanese UtilityModel Application (JU-A) No. 62-25944, and JP-A-6-130509, JP-A-6-95338,and JP-A-6-95267 are preferably used.

Employment of the color-developing agent in the present inventionensures that better color-developing ability(color-forming property) canbe obtained even in a short developing time and a developed color imagewhich has high stability against light, heat and humidity can beobtained.

Further, according to the color diffusion transfer type silver halidephotographic material and image-forming method of the present invention,good color-developing ability can be obtained even in a short developingtime and a transferred color image stable against light, heat andhumidity can also be obtained by using the color-developing agent andthe particular phenol type coupler.

EXAMPLES

Now, the present invention is described in more detail with reference tothe following examples, but the present invention is not limitedthereto.

Example 1

Image Receiving Element R101 having the constitution shown in Tables 1and 2 was made.

TABLE 1 Constitution of Image Receiving Element R101 Coated amountNumber of layer Additive (mg/m²) Sixth layer Water-soluble polymer(1)130 Water-soluble polymer(2) 35 Water-soluble polymer(3) 45 Potassiumnitrate 20 Anionic surfactant(1) 6 Anionic surfactant(2) 6 Amphotericsurfactant(1) 50 Stain-preventing agent(1) 7 Stain-preventing agent(2)12 Matting agent(1) 7 Fifth layer Gelatin 250 Water-soluble polymer(1)25 Anionic surfactant(3) 9 Hardener(1) 185 Forth layer Mordant(1) 1870Water-soluble polymer(2) 260 Water-soluble polymer(4) 1380 Dispersion oflatex(1) 600 Anionic surfactant(3) 25 Nonionic surfactant(1) 18Guanidine picolinate 2550 Sodium quinolinate 350 Third layer Gelatin 370Mordant(1) 300 Anionic surfactant(3) 12 Second layer Gelatin 700Mordant(1) 290 Water-soluble polymer(1) 55 Water-soluble polymer(2) 330Anionic surfactant(3) 30 Anionic surfactant(4) 7 High-boiling organicsolvent (1) 700 Brightening agent(1) 30 Stain-preventing agent(3) 32Guanidine picolinate 360 Potassium quinolinate 45 First layer Gelatin280 Water-soluble polymer(1) 12 Anionic surfactant(1) 14 Sodiummetaborate 35 Hardener(1) 185 Base(1) Polyethylene-Laminated PaperSupport (thickness 215 μm) The coated amount of dispersion of latex isin terms of the coated amount of solid content of latex.

TABLE 2 (continued from table 1) Constitution of Support (Base (1)) Filmthickness Name of layer Composition (μm) Surface Gelatin 0.1 undercoatlayer Surfact PE Low-density polyethylene 36.0 layer (Glossy) (Density0.923): 90.2 parts Surface-processed titanium oxide: 9.8 partsUltramarine: 0.001 parts Pulp Layer Fine quality paper 152.0 (LBKP/NBKP= 6/4, Density 1.053) Back-surface High-density polyethylene 27.0 PElayer (Density 0.955) (Matte) Back-surface Styrene/acrylate copolymer0.1 undercoat layer Colloidal silica Polystyrenesulfonic acid sodiumsalt 215.2

Anionic surfactant (1)

Anionic surfactant (2)

Anionic surfactant (3)

n = 12.6 Anionic surfactant (4)

x:y = 4:6 m = 6.8 Nonionic surfactant (1)

n = 85 Amphoteric sarfactant (1)

Brightening agent (1)

Mordant (1)

High-boiling solvent (1) C₂₈H_(46.9)Cl_(7.1) (EMPARA 40 (trade name:manufactured by Ajinomoto K.K.)) Stain-preventing agent (1)

Stain-preventing agent (2)

Stain-preventing agent (3)

Water-soluble polymer (1) Sumikagel L5-H (trade name: manufactured bySumitomo Kagaku CO.) Water-soluble polymer(2) Dextran (molecular weight70,000) Water-soluble polymer(3) κ(kappa)-Carrageenan (trade name:manufactured by Taito Co.) Water-soluble polymer(4) MP polymer MP-102(trade name: manufactured by Kuraray Co.) Dispersion of latex(1) LX-438(trade name: manufactured by Nippon Zeon Co.) Matting agent(1) SYLOID79(trade name: manufactured by Fuji Davisson Kagaku Co.)

Next, the methods of preparing light-sensitive elements are described.

First, the methods of preparing light-sensitive silver halide emulsionsare described. Light-Sensitive Silver Halide Emulsion (1) [for ared-sensitive emulsion layer]

Solution (I) having the composition shown in Table 4 was added to awell-stirred aqueous solution having the composition shown in Table 3,over 9 min at a constant flow rate, and before 10 sec of the addition ofSolution (I), Solution (II) was added over 9 min 10 sec at a constantflow rate. Then, after 36 min, Solution (III) having the compositionshown in Table 4 was added over 24 min at a constant flow rate, andsimultaneously with the addition of Solution (III), Solution (IV) wasadded over 25 min at a constant flow rate.

After washing with water and desalting (at a pH of 4.0 using SettlingAgent a) in a usual manner, 880 g of lime-processed ossein gelatin wasadded, the pH was adjusted to 6.0, and after the chemical sensitizationwas carried out optimally at 60° C. for 71 min by adding 12.8 g of aribonucleic acid decomposition product and 32 mg of trimethylthiourea,then, 2.6 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, 3.2 g of Dye(a), 5.1 g of KBr, and 2,6 g of stabilizer {circle around (1)} weresuccessively added, followed by cooling. In this way, 28.1 kg of amonodisperse cubic silver chlorobromide emulsion having an average grainsize of 0.35 μm was obtained.

TABLE 3 Composition H₂O 26300 cc Lime-processed gelatin 800 g KBr 12 gNaCl 80 g Compound(a) 1.2 g Temperature 53° C.

TABLE 4 Solution (I) Solution (II) Solution (III) Solution (IV) AgNO₃1200 g none 2800 g none KBr none 546 g none 1766 g NaCl none 144 g none96 g K₂IrCl₆ none 3.6 mg none none Total water to make water to makewater to make water to volume 6.5 liters 6.5 liters 10 liters make 10liters

Light-Sensitive Silver Halide Emulsion (2) [for a green-sensitiveemulsion layer]

Solutions (I) and (II) each having the composition shown in Table 6 wereadded simultaneously, to a well-stirred aqueous solution having thecomposition shown in Table 5, over 9 min at a constant flow rate. After5 min, Solutions (IV) and (III) each having the composition shown inTable 6 were simultaneously added thereto, at a constant flow rate over32 min. After the completion of the addition of Solutions (III) and(IV), 60 ml of a methanol solution of dyes (containing 360 mg of Dye(b1) and 73.4 mg of Dye (b2)) was added at a time.

After washing with water and desalting (at a pH of 4.0 using SettlingAgent a) in a usual manner, 22 g of lime-processed ossein gelatin wasadded, the pH and the pAg were adjusted to 6.0 and 7.6 respectively,then the chemical sensitization was carried out optimally at 60° C. byadding 1.8 mg of sodium thiosulfate and 180 mg of4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene, and then 90 mg of AntifoggingAgent (1) was added, followed by cooling. In this way, 635 g of amonodisperse cubic silver chlorobromide emulsion having an average grainsize of 0.30 μm was obtained.

TABLE 5 Composition H₂O 600 cc Lime-processed gelatin 20 g KBr 0.3 gNaCl 2 g Compound(a) 0.03 g Sulfuric acid (1N) 16 cc Temperature 46° C.

TABLE 5 Composition H₂O 600 cc Lime-processed gelatin 20 g KBr 0.3 gNaCl 2 g Compound(a) 0.03 g Sulfuric acid (1N) 16 cc Temperature 46° C.

Light-Sensitive Silver Halide Emulsion (3) [for a blue-sensitiveemulsion layer]

To a well-stirred aqueous solution having the composition shown in Table7, was added Solution (II) having the composition shown in Table 8 over30 min, and after 10 sec of the start of the addition of Solution (II)having the composition shown in Table 8 was added over 30 min. After 2min of the completion of the adding of solution (I), Solution (V) wasadded, also after 5 min of the completion of the adding of Solution(II), Solution (IV) was added, and then after 10 sec, Solution (III) wasadded over 27 min 50 sec and Solution (IV) was added over 28 min.

Then, after washing with water and desalting (at a pH of 3.9 usingSettling Agent b) in a usual manner, 1,230 g of lime-processed osseingelatin and 2.8 mg of Compound (b) were added, and the pH and the pAgwere adjusted to 6.1 and 8.4 respectively. Then, after the chemicalsensitization was carried out at 60° C. for optimally by adding 24.9 mgof sodium thiosulfate, 13.1 g of Dye (c) and 118 ml of Compound (c) wereadded successively, followed by cooling. The silver halide grains of theresulting emulsion were potato-like grains and had an average grain sizeof 0.53 μm and the yield was 30,700 g.

TABLE 7 Composition H₂O 29200 cc Lime-processed gelatin 1582 g KBr 127 gCompound(a) 0.66 g Temperature 72° C.

TABLE 8 Solution Solution Solution Solution Solution (I) (II) (III) (IV)(V) AgNO₃ 939 g none 3461 g none none KBr none 572 g none 2464 g none KInone none none none 22 g Total water to water to water to water to waterto volume make make make make make 6690 ml 6680 ml 9700 ml 9740 ml 4400ml

Next, the preparation methods of gelatin dispersions of hydrophobicadditives are described.

A gelatin dispersion of each of a yellow coupler, a magenta coupler, anda cyan coupler, and a developing agent, whose formulation is shown inTable 9 was prepared, respectively. That is, the oil phase componentswere dissolved by heating to about 70° C. to form a uniform solution,and, to the resultant solution, was added the aqueous phase componentsthat had been heated to about 60° C., followed by stirring to mix anddispersing by a homogenizer for 10 min at 10,000 rpm. To the resultantdescription, was added additional water, followed by stirring to obtaina uniform dispersion.

TABLE 9 Composition of dispersion Yellow Magenta Cyan Oil phase Cyancoupler{circle around (1)} none none  7.0 g Magenta coupler{circlearound (1)} none  7.0 g none Yellow coupler{circle around (1)}  7.0 gnone none Developing agent{circle around (1)} none none  5.6 gDeveloping agent{circle around (2)} none  5.6 g none Developingagent{circle around (3)}  5.6 g none none Auxiliary developing  0.51 g 0.51 g  0.51 g agent{circle around (1)} Antifoggant{circle around (5)} 0.25 g none none Antifoggant{circle around (2)} none  0.25 g  0.25 gHigh-boiling solvent{circle around (4)}  7.4 g  7.4 g  7.4 g Ethylacetate  15 cc  15 cc  15 cc Aqueous phase Lime-processed  10.0 g  10.0g  10.0 g gelatin Calcium nitrate  0.1 g  0.1 g  0.1 g Surfactant{circlearound (1)}  0.7 g  0.7 g  0.7 g Water 110 cc 110 cc 110 cc Additonalwater 110 cc 110 cc 110 cc Antiseptic{circle around (1)}  0.04 g  0.04 g 0.04 g

A gelatin dispersion of Antifoggant {circle around (4)} and ReducingAgent {circle around (1)} whose formulation is shown in Table 10 wasprepared. That is, the oil phase components were dissolved by heating toabout 60° C. to form a uniform solution, and, to the resultant solution,was added the aqueous phase components that had been heated to about 60°C., and after stirring and mixing them, the resultant mixture wasdispersed for 10 min at 10,000 rpm by a homogenizer, to obtain a uniformdispersion.

TABLE 10 Composition of dispersion Oil phase Antifoggant{circle around(4)} 0.16 g Reducing agent{circle around (1)} 1.3 g High-boilingsolvent{circle around (2)} 2.3 g High-boiling solvent{circle around (5)}0.2 g Surfactant{circle around (1)} 0.5 g Surfactant{circle around (4)}0.5 g Ethyl acetate 10.0 ml Aqueous Acid-processed gelatin 10.0 g phaseAntiseptic{circle around (1)} 0.004 g Calcium nitrate 0.1 g Water 35.0ml Additional water 104.4 ml

A dispersion of Polymer Latex (a) whose formulation is shown in Table 11was prepared. That is, while a mixed solution of Polymer Latex (a),Surfactant {circle around (5)}, and water was stirred, AnionicSurfactant {circle around (6)} was added thereto over 10 min, to obtaina uniform dispersion. The resulting dispersion was repeatedly dilutedwith water and concentrated using a ultrafiltration module(Ultrafiltration Module: ACV-3050, trade name, manufactured by AsahiChemical Industry Co., Ltd.) to bring the salt concentration of thedispersion to 1/9, thereby obtaining a dispersion.

TABLE 11 Composition of dispersion Polymer Latex (a) aqueous solution108 ml (solid content 13%) Surfactant{circle around (5)} 20 gSurfactant{circle around (6)} 600 ml Water 1232 ml

A gelatin dispersion of zinc hydroxide was prepared according to theformulation shown in Table 12. That is, after the components were mixedand dissolved, dispersing was carried out for 30 min in a mill usingglass beads having an average particle diameter of 0.75 mm. Then theglass beads were separated and removed, to obtain a uniform dispersion.

TABLE 12 Composition of dispersion Zinc hydroxide 15.9 g Carboxymethylcellulose 0.7 g Poly(sodium acrylate) 0.07 g Lime-processed gelatin 4.2g Water 100 ml Antiseptic{circle around (2)} 0.4 g

The preparation method of a gelatin dispersion of a matting agent thatwas added to the protective layer is described. A solution containingPMMA dissolved in methylene chloride was added, together with a smallamount of a surfactant, to gelatin, to obtain a uniform dispersionhaving an average particle size of 4.3 μm.

Using the above materials, Light-Sensitive Element 101 shown in Tables13 was prepared.

TABLE 13 Constitution of Main Materials of Light-Sensitive Element 101Added Number Name of amount of layer layer Additive (mg/m²) SeventhProtective Acid-processed gelatin 387 layer layer Matting agent (PMMAresin) 17 Surfactant{circle around (2)} 6 Surfactant{circle around (3)}20 Dispersion of Polymer Latex (a) 10 Sixth Intermediate Lime-processedgelatin 862 layer layer Antifoggant{circle around (4)} 7 Reducingagent{circle around (1)} 57 High-boiling solvent{circle around (2)} 101High-boiling solvent{circle around (5)} 9 Surfactant{circle around (1)}21 Surfactant{circle around (4)} 21 Water-soluble polymer{circle around(1)} 5 Zinc hydroxide 558 Calcium nitrate 6 Fifth Blue-light-Lime-processed gelatin 587 layer sensitive Light-sensitive silver halide399 layer emulsion(3) Yellow coupler{circle around (1)} 410Coior-developing agent{circle around (3)} 328 Antifoggant{circle around(5)} 15 High-boiling solvent{circle around (4)} 433 Surfactant{circlearound (1)} 12 Water-soluble polymer{circle around (1)} 40 Auxiliarydeveloping agent{circle around (1)} 30 Forth Intermediate Lime-processedgelatin 862 layer layer Antifoggant{circle around (4)} 7 Reducingagent{circle around (1)} 57 High-boiling solvent{circle around (2)} 101High-boiling solvent{circle around (5)} 9 Surfactant{circle around (1)}21 Surfactant{circle around (4)} 21 Water-soluble polymer{circle around(1)} 4 Zinc hydroxide 341 Calcium nitrate 8

TABLE 14 (continued from Table 13) Constitution of Main Materials ofLight-Sensitive Element 101 Third Green-light- Lime-processed gelatin452 layer sensitive Light-sensitive silver halide 234 layer emulsion(2)Magenta coupler{circle around (1)} 420 Developing agent{circle around(2)} 336 Antifoggant{circle around (2)} 15 High-boiling solvent{circlearound (4)} 444 Surfactant{circle around (1)} 12 Water-solublepolymer{circle around (1)} 10 Auxiliary developing agent{circle around(1)} 30 Second Intermediate Lime-processed gelatin 862 layer layerAntifoggant{circle around (4)} 7 Reducing agent{circle around (1)} 57High-boiling solvent{circle around (2)} 101 High-boiling solvent{circlearound (5)} 9 Surfactant{circle around (1)} 21 Surfactant{circle around(4)} 21 Water-soluble polymer{circle around (1)} 10 Calcium nitrate 6First Red-light- Lime-processed gelatin 373 layer sensitiveLight-sensitive silver halide 160 layer emulsion(1) Cyan coupler{circlearound (1)} 390 Developing agent{circle around (1)} 312Antifoggant{circle around (2)} 14 High-boiling solvent{circle around(4)} 412 Surfactant{circle around (1)} 11 Water-soluble polymer{circlearound (2)} 25 Hardener{circle around (1)} 45 Auxiliary developingagent{circle around (1)} 30 Support (a support made byaluminum-evaporation on a PET of 20 μm and further surface-undercoatingwith gelatin.)

Next, light sensitive elements 103-108 were made in the same mannerexcept that developing agents represented by the formula (1) of thepresent invention and couplers shown in Table 15 were used in place ofthe developing agent and coupler used in the first, third and fifthlayers of the above light-sensitive material 101. The developing agentsand couplers used here are shown in Table 15. In addition, alight-sensitive element 102 was made using compounds described inJP-A-09-152702.

Then, using each light-sensitive material and the image-receivingelement R101, obtained as the above, an image was output at 83° C. for10 seconds by a Pictrostat 330 (trade name) manufactured by Fuji PhotoFilm Co., Ltd.

The images output from the light-sensitive elements 103-108 were sharp(vivid) color images, indicating that the use of the compounds of thepresent invention ensured the provision of an image having highsharpness.

The maximum density and the minimum density, of the images thusobtained, were measured using a reflecting densitometer X-rite 304manufactured by X-rite Co. The results are shown in Table 16.

When the compounds of the present invention were used, as is clear fromTable 16, excellent color formation efficiency was obtained in a shortdeveloping time and the resulting image was stable under variousconditions with respect to light, heat, humidity, and the like.

TABLE 15 Light- Yellow Magenta Cyan sensi- Deve- Deve- Deve- tive lopingloping Cou- loping material Coupler agent Coupler agent pler agent 101Yellow Deve- Magenta Deve- Cyan Deve- coupler loping coupler lopingcoupler loping {circle around (1)} agent{circle around (3)} {circlearound (1)} agent{circle around (2)} {circle around (1)} agent{circlearound (1)} 102 Yellow a Magenta a Cyan a coupler coupler{circle around(1)} coupler {circle around (1)} {circle around (1)} 103 Yellow R-1Magenta R-1 Cyan R-1 coupler coupler{circle around (1)} coupler {circlearound (1)} {circle around (1)} 104 C-14 R-2 C-38 R-2 C-32 R-2 105 C-4R-4 C-41 R-1 C-32 R-4 106 C-14 R-5 C-50 R-1 C-37 R-5 107 C-23 R-7 C-28R-16 C-31 R-16 108 C-4 R-1 C-38 R-1 C-29 R-1 Note) a represents acompound D-7 described in JP-A-9-152702.

TABLE 16 Light- Yellow Magenta Cyan sensitive Maximum Minimum MaximumMinimum Maximum Minimum material density density density density densitydensity Remarks 101 0.98 0.18 1.13 0.13 1.22 0.19 Comparative example102 1.12 0.14 1.26 0.14 1.38 0.16 Comparative example 103 1.68 0.14 1.880.15 1.81 0.16 This invention 104 1.58 0.16 1.81 0.13 1.80 0.16 Thisinvention 105 1.71 0.15 1.80 0.13 1.76 0.16 This invention 106 1.66 0.141.91 0.12 1.72 0.18 This invention 107 1.81 0.15 1.78 0.14 1.94 0.17This invention 108 1.88 0.16 2.01 0.14 2.11 0.18 This invention

Example 2

Light-Sensitive Element 201 was prepared in the ing manner.

First, the method of preparing a light-sensitive silver halide emulsionis described. Light-Sensitive Silver Halide Emulsion (4) [For FifthLayer (680 nm light-sensitive layer)]

To a well-stirred aqueous solution having the composition shown in Table17, were added Solutions (I) and (I) each having the composition shownin Table 18, simultaneously over 13 min, and after 10 min, Solutions(III) and (IV) each having the composition shown in Table 18 were addedover 33 min.

TABLE 17 Composition H₂O 620 cc Lime-processed gelatin 20 g KBr 0.3 gNaC1 2 g Silver halide solvent{circle around (1)} 0.03 g Sulfuric acid(1N) 16 cc Temperature 45° C.

TABLE 17 Composition H₂O 620 cc Lime-processed gelatin 20 g KBr 0.3 gNaC1 2 g Silver halide solvent{circle around (1)} 0.03 g Sulfuric acid(1N) 16 cc Temperature 45° C.

Further, after 13 min from the start of addition of solution (III), 150cc of an aqueous solution containing 0.35% of sensitizing dye {circlearound (1)} was added over 27 min.

After washing with water and desalting (that was carried out usingSettling Agent a, at a pH of 4.1) in a usual manner, 22 g oflime-processed ossein gelatin was added, and after adjusting the pH andpAg to 6.0 and 7.9 respectively, the chemical sensitization was carriedout at 60° C. The compounds used in the chemical sensitization are shownin Table 19. In this way, 630 g of a monodisperse cubic silverchlorobromide emulsion having a deviation coefficient of 10.2% and anaverage grain size of 0.20 μm was obtained.

TABLE 19 Chemicals used in chemical Added sensitization amount4-hydroxy-6-methyl-1,3,3a,7- 0.36 g tetrazaindene Sodium thiosulfate6.75 mg Antifoggant{circle around (1)} 0.11 g Antiseptic{circle around(1)} 0.07 g Antiseptic{circle around (2)} 3.31 g

Light-Sensitive Silver Halide Emulsion (5) [For Third Layer (750-nmlight-sensitive layer)]

To a well-stirred aqueous solution having the composition shown in Table20, were added Solutions (I) and (II) each having the composition shownin Table 21, simultaneously over 18 min, and after 10 min, Solutions(III) and (IV) each having the composition shown in Table 21 were addedover 24 min.

TABLE 20 Composition H₂O 620 cc Lime-processed gelatin 20 g KBr 0.3 gNaCl 2 g Silver halide solvent{circle around (1)} 0.03 g Sulfuric acid(1N) 16 cc Temperature 45° C.

TABLE 20 Composition H₂O 620 cc Lime-processed gelatin 20 g KBr 0.3 gNaCl 2 g Silver halide solvent{circle around (1)} 0.03 g Sulfuric acid(1N) 16 cc Temperature 45° C.

After washing with water and desalting (that was carried out usingSettling Agent b at a pH of 3.9) in a usual manner, 22 g oflime-processed ossein gelatin from which calcium had been removed (thecalcium content: 150 ppm or less) was added, re-dispersing was made at40° C., 0.39 g of 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was added,and the pH and pAg were adjusted to 6.9 and 7.8 respectively. Thereafterthe chemical sensitization was carried out at 70° C. using the chemicalsshown in Table 22. At the end of the chemical sensitization, SensitizingDye {circle around (2)} in the form of a methanol solution (the solutionhaving the composition shown in Table 23) was added. After the chemicalsensitization, the temperature was lowered to 40° C. and then 200 g of agelatin dispersion of the later-described Stabilizer {circle around (1)}was added, followed by stirring well, and in this way, 938 g of amonodisperse cubic silver chlorobromide emulsion having a deviationcoefficient of 12.6% and an average grain size of 0.25 μm was obtained.In this connection, the emulsion for a 750 nm light-sensitive layer hadspectral sensitivity of the J-band type.

TABLE 22 Chemicals used in chemical Added sensitization amount4-hydroxy-6-methyl-1,3,3a,7- 0.39 g tetrazaindene Triethylthiourea 3.3mg Nucleic acid decomposition 0.39 g product NaCl 0.15 g KI 0.12 gAntifoggant{circle around (2)} 0.10 g Antiseptic{circle around (1)} 0.07g

TABLE 22 Chemicals used in chemical Added sensitization amount4-hydroxy-6-methyl-1,3,3a,7- 0.39 g tetrazaindene Triethylthiourea 3.3mg Nucleic acid decomposition 0.39 g product NaCl 0.15 g KI 0.12 gAntifoggant{circle around (2)} 0.10 g Antiseptic{circle around (1)} 0.07g

Light-Sensitive Silver Halide Emulsion (6) [For First Layer (810nmlight-sensitive layer)]

To a well-stirred aqueous solution having the composition shown in Table24, were added Solutions (I) and (II) each having the composition shownin Table 25, simultaneously over 18 min, and after 10 min, Solutions(III) and (IV) each having the composition shown in Table 25 were addedover 24 min.

TABLE 24 Composition H₂O 620 cc Lime-processed gelatin 20 g KBr 0.3 gNaC1 2 g Silver halide solvent{circle around (1)} 0.03 g Sulfuric acid(1N) 16 cc Temperature 50° C.

TABLE 24 Composition H₂O 620 cc Lime-processed gelatin 20 g KBr 0.3 gNaC1 2 g Silver halide solvent{circle around (1)} 0.03 g Sulfuric acid(1N) 16 cc Temperature 50° C.

After washing with water and desalting (that was carried out usingSettling Agent a at a pH of 3.8) in a usual manner, 22 g oflime-processed ossein gelatin was added, and after adjusting the pH andpAg to 7.4 and 7.8 respectively, the chemical sensitization was carriedout. The compounds used in the chemical sensitization are shown in Table26. At the end of the chemical sensitization, Sensitizing Dye {circlearound (3)} in the form of a methanol solution (same way to SensitizingDye {circle around (2)} shown in Table 23) was added. In this way, 680 gof a monodisperse cubic silver chlorobromide emulsion having a deviationcoefficient of 9.7% and an average grain size of 0.32 μm was obtained.

TABLE 26 Chemicals used in chemical Added sensitization amount4-hydroxy-6-methyl-1,3,3a,7- 0.38 g tetrazaindene Triethylthiourea 3.1mg Antifoggant{circle around (2)} 0.19 g Antiseptic{circle around (1)}0.07 g Antiseptic{circle around (2)} 3.13 g

Next, the preparation method of a gelatin dispersion of colloidal silveris described.

To a well-stirred aqueous solution having the composition shown in Table27, was added a Solution having the composition shown in Table 28, over24 min. Thereafter, the washing with water using Settling Agent a wascarried out, then 43 g of lime-processed ossein gelatin was added, andthe pH was adjusted to 6.3. In this way, 512 g of a dispersion havingaverage grain size of 0.02 μm, and containing silver 2% and gelatin 6.8%was obtained.

TABLE 27 Composition H₂O 620 cc Dextrin 16 g NaOH (5N) 41 cc Temperature30° C.

TABLE 27 Composition H₂O 620 cc Dextrin 16 g NaOH (5N) 41 cc Temperature30° C.

Next, the preparation methods of gelatin dispersions of hydrophobicadditives are described.

A gelatin dispersion of each of a yellow coupler, a magenta coupler, acyan coupler, and a color-developing agent whose formulation is shown inTable 29, was prepared, respectively. That is, the oil phase componentswere dissolved by heating to about 70° C., to form a uniform solution,and to the resultant solution, was added the aqueous phase componentsthat had been heated to about 60° C., followed by stirring to mix anddispersing by a homogenizer for 10 min at 10,000 rpm. To the resultantdispersion, was added additional water, followed by stirring, to obtaina uniform dispersion.

TABLE 29 Composition of dispersion Yellow Magenta Cyan Oil Cyancoupler{circle around (2)} none none 7.0 g phase Magenta coupler{circlearound (2)} none 7.0 g none Yellow coupler{circle around (2)} 7.0 g nonenone Developing agent{circle around (4)} none none 5.6 g Developingagent{circle around (4)} none 5.6 g none Developing agent{circle around(4)} 5.6 g none none Auxiliary developing 0.51 g 0.51 g 0.51 gagent{circle around (1)} Antifoggant{circle around (5)} 0.25 g none noneAntifoggant{circle around (2)} none 0.25 g 0.25 g High-boilingsolvent{circle around (4)} 7.4 g 7.4 g 7.4 g Dye(a) 1.1 g none 0.5 gEthyl acetate 15 cc 15 cc 15 cc Aqueo- Lime-processed 10.0 g 10.0 g 10.0g us gelatin phase Calcium nitrate 0.1 g 0.1 g 0.1 g Surfactant{circlearound (1)} 0.2 g 0.2 g 0.2 g Water 110 cc 110 cc 110 cc Additionalwater 110 cc 110 cc 110 cc Antiseptic{circle around (1)} 0.04 g 0.04 g0.04 g

A gelatin dispersion of Antifoggant {circle around (4)} and ReducingAgent {circle around (1)} whose formulation is shown in Table 30 wasprepared. That is, the oil phase components were dissolved by heating toabout 60° C. to form a uniform solution, to the resultant solution, wasadded the aqueous phase components that had been heated to about 60° C.,and after stirring and mixing them, the resultant mixture was dispersedfor 10 min at 10,000 rpm by a homogenizer, to obtain a uniformdispersion.

TABLE 30 Composition of dispersion Oil Antifoggant{circle around (4)}0.16 g phase Reducing agent{circle around (1)} 1.3 g High-boilingsolvent{circle around (2)} 2.3 g High-boiling solvent{circle around (5)}0.2 g Surfactant{circle around (1)} 0.5 g Surfactant{circle around (4)}0.5 g Ethyl acetate 10.0 ml Aqueous Acid-processed gelatin 10.0 g phaseAntiseptic{circle around (1)} 0.004 g Calcium nitrate 0.1 g Water 35.0ml Additional Water 104.4 ml

A gelatin dispersion of Reducing Agent {circle around (2)} whoseformulation is shown in Table 31 was prepared. That is, the oil phasecomponents were dissolved by heating to about 60° C. to form a uniformsolution, to the resultant solution, was added the aqueous phasecomponents that had been heated to about 60° C., and after stirring andmixing them, the resultant mixture was dispersed for 10 min at 10,000rpm by a homogenizer, to obtain a uniform dispersion. From thethus-obtained dispersion, ethyl acetate was removed off using a vacuumorganic solvent removing apparatus.

TABLE 31 Composition of dispersion Oil Reducing agent{circle around (2)}7.5 g phase High-boiling solvent{circle around (1)} 4.7 gSurfactant{circle around (1)} 1.9 g Ethyl acetate 14.4 ml AqueousAcid-processed gelatin 10.0 g phase Antiseptic{circle around (1)} 0.02 gGentamicin 0.04 g Sodium bisulfite 0.1 g Water 136.7 ml

A dispersion of Polymer Latex (a) whose formulation is shown in Table 32was prepared. That is, while a mixed solution of Polymer Latex (a),Surfactant {circle around (5)}, and water whose amounts are shown inTable 32 was stirred, Anionic Surfactant {circle around (6)} was addedthereto, over 10 min, to obtain a uniform dispersion. The resultingdispersion was repeatedly diluted with water and concentrated using aultrafiltration module (Ultrafiltration Module: ACV-3050, trade name,manufactured by Asahi Chemical Industry Co., Ltd.), to bring the saltconcentration of the dispersion to 1/9, thereby obtaining a dispersion.

TABLE 32 Composition of dispersion Polymer Latex (a) aqueous solution108 ml (solid content 13%) Surfactant{circle around (5)} 20 gSurfactant{circle around (6)} 600 ml Water 1232 ml

A gelatin dispersion of Stabilizer {circle around (1)} whose formulationis shown in Table 33 was prepared. That is, the oil phase componentswere dissolved at room temperature to form a uniform solution, to theresultant solution, was added the aqueous phase components that had beenheated to about 40° C., and after stirring and mixing them, theresultant mixture was dispersed for 10 min at 10,000 rpm by ahomogenizer. To the resultant dispersion, was added additional water,followed by stirring, thereby obtaining a uniform dispersion.

TABLE 33 Composition of dispersion Oil phase Stabilizer{circle around(1)} 4.0 g Sodium hydroxide 0.3 g Methanol 62.8 g Antiseptic{circlearound (2)} 0.8 g Aqueous Gelatin from which calcium 10.0 g phase hadbeen removed (Ca content 100 ppm or less) Antiseptic{circle around (1)}0.04 g Water 320 ml

A gelatin dispersion of zinc hydroxide was prepared according to theformulation shown in Table 34. That is, after the components were mixedand dissolved, dispersing was carried out for 30 min in a mill, usingglass beads having an average particle diameter of 0.75 mm. Then theglass beads were separated and removed off, to obtain a uniformdispersion.

TABLE 34 Composition of dispersion Zinc hydroxide 15.9 g Carboxymethylcellulose 0.7 g Poly(sodium acrylate) 0.07 g Lime-processed gelatin 4.2g Water 100 ml Antiseptic{circle around (2)} 0.4 g

Next, the preparation method of a gelatin dispersion of a matting agentthat was added to the protective layer is described. A solutioncontaining PMMA dissolved in methylene chloride was added, together witha small amount of a surfactant, to gelatin, and obtained a uniformdispersion having an average particle size of 4.3 μm.

Using the above materials, Light-Sensitive Element 201 shown in Tables35 was prepared.

TABLE 35 Constitution of Main Materials of Light-Sensitive Element 201Number Name of Added amount of layer layer Additive (mg/m²) SeventhProtective Acid-processed gelatin 442 layer layer Reducing agent{circlearound (2)} 47 High-boiling solvent{circle around (1)} 30 Colloidalsilver grains 2 Matting agent(PMMA resin) 17 Surfactant{circle around(1)} 16 Surfactant{circle around (2)} 9 Surfactant{circle around (3)} 2Sixth Intermediate Lime-processed gelatin 862 layer layerAntifoggant{circle around (4)} 7 Reducing agent{circle around (1)} 57High-boiling solvent{circle around (2)} 101 High-boiling solvent{circlearound (5)} 9 Surfactant{circle around (1)} 21 Surfactant{circle around(4)} 21 Dispersion of Polymer Latex a 5 Water-soluble polymer{circlearound (1)} 4 Calcium nitrate 6 Fifth Red-light- Lime-processed gelatin452 layer sensitive Light-sensitive silver halide 301 layer emulsion(4)Magenta coupler{circle around (2)} 420 Developing agent{circle around(4)} 336 Antifoggant{circle around (2)} 15 High-boiling solvent{circlearound (4)} 444 Surfactant{circle around (1)} 12 Water-solublepolymer{circle around (1)} 10 Auxiliary developing agent{circle around(1)} 30 Forth Intermediat Lime-processed gelatin 862 layer layerAntifoggant{circle around (4)} 7 Reducing agent{circle around (1)} 57High-boiling solvent{circle around (2)} 101 High-boiling solvent{circlearound (5)} 9 Surfactant{circle around (1)} 21 Surfactant{circle around(4)} 21 Dispersion of Polymer Latex a 5 Water-soluble polymer{circlearound (1)} 4 Calcium nitrate 6

TABLE 36 (continued from Table 35) Constitution of Main Materials ofLight- Sensitive Element 201 Third Second Lime-processed gelatin 373layer infrared-light- Light-sensitive silver 106 sensitive layer halideemulsion(5) Cyan coupler{circle around (2)} 390 Developing agent{circlearound (4)} 312 Antifoggant{circle around (2)} 14 High-boilingsolvent{circle around (4)} 412 Surfactant{circle around (1)} 11Water-soluble polymer{circle around (1)} 11 Auxiliary developingagent{circle around (1)} 30 Second Intermediate Lime-processed gelatin862 layer layer Antifoggant{circle around (4)} 7 Reducing agent{circlearound (1)} 57 High-boiling solvent{circle around (2)} 101 High-boilingsolvent{circle around (5)} 9 Surfactant{circle around (1)} 21Surfactant{circle around (4)} 21 Water-soluble polymer{circle around(2)} 25 Zinc hydroxide 750 Calcium nitrate 6 First First infrared-Lime-processed gelatin 587 layer light- Light-sensitive silver 311sensitive layer halide emulsion(6) Yellow coupler{circle around (2)} 410Developing agent{circle around (4)} 328 Antifoggant{circle around (5)}15 High-boiling solvent{circle around (4)} 433 Surfactant{circle around(1)} 12 Water-soluble polymer{circle around (2)} 40 Hardener{circlearound (1)} 45 Auxiliary developing agent{circle around (1)} 30Support(a support made by aluminum- evaporation on a PET of 20 μm andfurther surface-undercoating with gelatin.)

Next, light-sensitive elements 203-208 were made in the same mannerexcept that developing agents represented by the formula (1) of thepresent invention and couplers shown in Table 37 were used in place ofthe developing agent and coupler used in the first, third and fifthlayers of the above light-sensitive material 201. The developing agentsand couplers used here are shown in Table 37. In addition, alight-sensitive element 202 was made using compounds described inJP-A-09-152702.

Then, using each light-sensitive material obtained as the above and theimage-receiving element R101 prepared in the same manner as in Example1, an image was output at 83° C. for 30 seconds by a PG-3000 (tradename) manufactured by Fuji Photo Film Co., Ltd.

The images output from the light-sensitive elements 203-208 weresharp(vivid) color images, indicating that the use of the compounds ofthe present invention ensured the provision of an image having highsharpness.

The maximum density and the minimum density, of the images thusobtained, were measured using a reflecting densitometer X-rite 304manufactured by X-rite Co. The results are shown in Table 38.

When the compounds of the present invention were used, as is clear fromTable 38, excellent color formation efficiency was obtained in a shortdeveloping time, the resulting image was stable under various conditionswith respect to light, heat, humidity, and the like.

TABLE 37 Yellow Magenta Cyan Light- Deve- Deve- Deve- sensitive lopingloping loping material Coupler agent Coupler agent Coupler agent 201Yellow Deve- Magenta Deve- Cyan Deve- coupler loping coupler lopingcoupler loping {circle around (2)} agent {circle around (2)} agent{circle around (2)} agent{circle around (4)} {circle around (4)} {circlearound (4)} 202 Yellow a* Magenta a Cyan a coupler coupler coupler{circle around (2)} {circle around (2)} {circle around (2)} 203 YellowR-1 Magenta R-1 Cyan R-1 coupler coupler coupler {circle around (2)}{circle around (2)} {circle around (2)} 204 C-14 R-2 C-38 R-2 C-32 R-2205 C-4 R-4 C-41 R-1 C-32 R-4 206 C-14 R-5 C-50 R-1 C-37 R-5 207 C-23R-7 C-28 R-16 C-31 R-16 208 C-4 R-1 C-38 R-1 C-29 R-1 Note)*a is acompound D-7 described in JP-A-9-152702.

TABLE 38 Light- Yellow Magenta Cyan sensitive Maximum Minimum MaximumMinimum Maximum Minimum material density density density density densitydensity Remarks 201 1.20 0.16 1.28 0.14 1.40 0.16 Comparative example202 1.22 0.14 1.36 0.14 1.38 0.15 Comparative example 203 1.80 0.14 1.950.14 1.88 0.15 This invention 204 1.78 0.13 1.96 0.14 1.89 0.15 Thisinvention 205 1.81 0.16 1.99 0.13 1.81 0.16 This invention 206 1.80 0.162.01 0.14 1.95 0.16 This invention 207 2.00 0.15 1.88 0.16 2.00 0.16This invention 208 2.08 0.15 2.11 0.14 2.14 0.15 This invention

Example 3

In the method described in Example 1 of JP-A-09-152702, the developingagents (Exemplified compounds R-1, R-2, R-5, R-11, R-15 and R-23) of thepresent invention were used in place of the compound example D-7 and analkali treating solution was used to carry out developing treatment. Asa consequence, images were obtained which were superior in colorformation efficiency and had good storage stability, similar in theExamples 1 and 2.

Example 4

Light sensitive elements 401-406 were made in the same manner exceptthat developing agents represented by the formula (2) of the presentinvention and couplers shown in Table 39 were used in place of thedeveloping agent and coupler used in the first, third and fifth layersof the above light-sensitive material 101 used in Example 1. Thedeveloping agents and couplers used here are shown in Table 39. Inaddition, a light-sensitive element 102 was made using compoundsdescribed in JP-A-09-152702.

Then, using each light-sensitive material obtained as the above and theimage-receiving element R101 prepared in the same manner as in Example1, an image was output at 83° C. for 20 seconds by a Pictrostat 330(trade name) manufactured by Fuji Photo Film Co., Ltd.

The images output from the light-sensitive elements 401-406 were sharp(vivid) color images, indicating that the use of the compounds of thepresent invention ensured the provision of an image having highsharpness.

The maximum density and the minimum density, of the images thusobtained, were measured using a reflecting densitometer X-rite 304manufactured by X-rite Co. The results are shown in Table 40.

When the compounds of the present invention were used, as is clear fromTable 40, excellent color formation efficiency was obtained in a shortdeveloping time and the resulting image was stable under variousconditions with respect to light, heat, humidity, and the like.

TABLE 39 Yellow Magenta Cyan Light- Deve- Deve- Deve- sensitive lopingloping loping material Coupler agent Coupler agent Coupler agent 101Yellow Deve- Magenta Deve- Cyan Deve- coupler loping coupler lopingcoupler loping {circle around (1)} agent {circle around (1)} agent{circle around (1)} agent{circle around (1)} {circle around (3)} {circlearound (2)} 102 Yellow a* Magenta a Cyan a coupler coupler {circlearound (1)} {circle around (1)} {circle around (1)} 401 Yellow R-101Magenta R-101 Cyan R-101 coupler coupler coupler {circle around (1)}{circle around (1)} {circle around (1)} 402 C-14 R-102 C-38 R-102 C-32R-102 403 C-4 R-103 C-41 R-101 C-32 R-114 404 C-14 R-106 C-50 R-111 C-37R-123 405 C-23 R-107 C-28 R-111 C-31 R-116 406 C-4 R-101 C-38 R-101 C-29R-101 Note)*a is a compound D-7 described in JP-A-9-152702.

TABLE 40 Light- Yellow Magenta Cyan sensitive Maximum Minimum MaximumMinimum Maximum Minimum material density density density density densitydensity Remarks 101 0.80 0.14 1.00 0.13 1.01 0.15 Comparative example102 1.01 0.14 1.16 0.12 1.25 0.14 Comparative example 401 1.21 0.13 1.410.11 1.41 0.13 This invention 402 1.26 0.13 1.51 0.13 1.39 0.14 Thisinvention 403 1.24 0.13 1.40 0.13 2.36 0.15 This invention 404 1.66 0.141.91 0.12 1.51 0.14 This invention 405 1.61 0.13 2.24 0.12 1.44 0.12This invention 406 1.24 0.12 1.61 0.14 1.41 0.14 This invention

Example 5

Light sensitive elements 501-506 were made in the same manner exceptthat developing agents represented by the formula (2) of the present.invention and couplers shown in Table 41 were used in place of thedeveloping agent and coupler used in the first, third and fifth layersof the above light-sensitive material 201 used in Example 2. Thedeveloping agents and couplers used here are shown in Table 41. Inaddition, a light-sensitive element 202 was made using compoundsdescribed in JP-A-09-152702.

Then, using each light-sensitive material obtained as the above and theimage-receiving element R101 prepared in the same manner as in Example1, an image was output at 83° C. for 17 seconds by a PG-3000 (tradename) manufactured by Fuji Photo Film Co., Ltd.

The images output from the light-sensitive elements 501-506 weresharp(vivid) color images, indicating that the use of the compounds ofthe present invention ensured the provision of an image having highsharpness.

The maximum density and the minimum density, of the images thusobtained, were measured using a reflecting densitometer X-rite 304manufactured by x-rite Co. The results are shown in Table 42.

When the compounds of the present invention were used, as is clear fromTable 42, excellent color formation efficiency was obtained in a shortdeveloping time and the resulting image was stable under variousconditions with respect to light, heat, humidity, and the like.

TABLE 41 Yellow Magenta Cyan Light- Deve- Deve- Deve- sensitive lopingloping loping material Coupler agent Coupler agent Coupler agent 201Yellow Deve- Magenta Deve- Cyan Deve- Coupler loping coupler lopingcoupler loping {circle around (2)} agent {circle around (2)} agent{circle around (2)} agent {circle around (4)} {circle around (4)}{circle around (4)} 202 Yellow a* Magenta a Cyan a coupler couplercoupler {circle around (2)} {circle around (2)} {circle around (2)} 501Yellow R-101 Magenta R-101 Cyan R-101 coupler coupler coupler {circlearound (2)} {circle around (2)} {circle around (2)} 502 C-14 R-102 C-38R-102 C-32 R-102 503 C-4 R-103 C-41 R-101 C-32 R-114 504 C-14 R-106 C-50R-111 C-37 R-123 505 C-23 R-107 C-28 R-111 C-31 R-116 506 C-4 R-101 C-38R-101 C-29 R-101 Note)*a is a compound D-7 described in JP-A-9-152702.

TABLE 42 Light- Yellow Magenta Cyan sensitive Maximum Minimum MaximumMinimum Maximum Minimum material density density density density densitydensity Remarks 201 0.91 0.14 1.14 0.13 1.14 0.15 Comparative example202 1.13 0.14 1.25 0.12 1.36 0.14 Comparative example 501 1.31 0.13 1.640.14 1.61 0.12 This invention 502 1.33 0.12 1.81 0.13 1.62 0.13 Thisinvention 503 1.30 0.13 1.63 0.13 2.55 0.15 This invention 504 1.71 0.142.11 0.12 1.81 0.14 This invention 505 1.88 0.13 2.38 0.12 1.64 0.12This invention 506 1.41 0.12 1.84 0.14 1.49 0.14 This invention

Example 6

In the method described in Example 1 of JP-A-09-152702, the developingagents (Exemplified compounds R-101, R-102, R-106, R-107, R-111 andR-114) of the present invention were used in place of the compoundexample D-7 and an alkali treating solution was used to carry outdeveloping treatment. As a consequence, images were obtained which weresuperior in color formation efficiency and had good storage stability,similar in the Examples 4 and 5.

Example 7

As shown in Table 43, light sensitive elements 701 to 707 were made inthe same manner except that developing agents and couplers representedby the formula (3) and (4) as defined in the present invention were usedin place of the developing agent and coupler used in the third layer ofthe above light-sensitive material 101 used in Example 1.

Then, using each light-sensitive material obtained as the above and theimage-receiving element R101 prepared in the same manner as in Example1, an image was output at 80° C. for 20 seconds by a Pictrostat 330(trade name) manufactured by Fuji Photo Film Co., Ltd.

The images output from the light-sensitive elements 701-707 weresharp(vivid) color images, indicating that the use of the compounds asdefined in the present invention ensured the provision of an imagehaving high sharpness.

The magenta maximum density and magenta minimum density, of the imagesthus obtained, were measured using a reflecting densitometer X-rite 304manufactured by X-rite Co. The results are shown in Table 43.

When the compounds as defined in the present invention were used, as isclear from Table 43, excellent color formation efficiency was obtainedin a short developing time and the resulting image was stable undervarious conditions with respect to light, heat, humidity and the like.

TABLE 43 Light- Developing sensi- agent for Coupler for Maxi- Mini- tivemagenta magenta mum mum material color color density density Remarks 101Developing Magenta 1.21 0.13 Comparative agent{circle around (2)}coupler example {circle around (1)} 701 R-201 MC-1 1.75 0.12 Thisinvention 702 R-201 MC-2 1.81 0.12 This invention 703 R-201 MC-16 2.000.13 This invention 704 R-202 MC-1 1.55 0.10 This invention 705 R-202MC-2 1.51 0.11 This invention 706 R-212 MC-4 1.88 0.13 This invention707 R-213 MC-17 1.65 0.11 This invention

Example 8

As shown in Table 44, light sensitive elements 801 to 807 were made inthe same manner except that developing agents and couplers representedby the formula (3) and (4) as defined in the present invention were usedin place of the developing agent and coupler used in the fifth layer ofthe above light-sensitive material 201 used in Example 2.

Then, using thus obtained each light-sensitive material obtained as theabove and the image-receiving element R101 prepared in the same manneras in Example 1, an image was output at 83° C. for 30 seconds by aPG-3000 (trade name) manufactured by Fuji Photo Film Co., Ltd.

The images output from the light-sensitive elements 801-807 weresharp(vivid) color images, indicating that the use of the compounds ofthe present invention ensured the provision of an image having highsharpness.

The magenta maximum density and magenta minimum density, of the imagesthus obtained, were measured using a reflecting densitometer X-rite 304manufactured by X-rite Co. The results are shown in Table 44.

When the compounds defined in the present invention were used, as isclear from Table 44, excellent color formation efficiency was obtainedin a short developing time and the resulting image was stable undervarious conditions with respect to light, heat, humidity, and the like.

TABLE 44 Light- Developing sensi- agent for Coupler for Maxi- Mini- tivemagenta magenta mum mum material color color density density Remarks 201Developing Magenta 1.30 0.14 Comparative agent{circle around (4)}coupler example {circle around (2)} 801 R-201 MC-1 1.80 0.12 Thisinvention 802 R-201 MC-2 1.85 0.13 This invention 803 R-201 MC-16 1.950.10 This invention 804 R-202 MC-1 1.52 0.10 This invention 805 R-202MC-2 1.46 0.11 This invention 806 R-212 MC-4 1.89 0.13 This invention807 R-213 MC-17 1.62 0.12 This invention

Example 9

The developing agents (Exemplified compounds R-201, R-202, R-205, R-211,R-215 and R-223) and couplers (Exemplified compounds MC-1, MC-2, MC-4,MC-8, MC-11 and MC-16) which are defined in the present invention, wereused in place of the compound example D-7 and ExM of the sample 202according to the method described in an Example 1 of P-A-9-152702, anddeveloping treatment was carried out using an alkali solution, to obtaina excellent image.

Having described our invention as related to the present embodiments, itis our intention that the invention not be limited by any of the detailsof the description, unless otherwise specified, but rather be construedbroadly within its spirit and scope as set out in the accompanyingclaims.

What we claim is:
 1. A color-developing agent represented by thefollowing formula (1):

wherein X represents a substituent that has, as a substituent on thesubstituent, at least one substituent represented by —COOH, —NHSO₂R,—SO₂NHR, —SO₂NHCOR, —CONHSO₂R, in which R represents an alkyl group, anaryl group or an aromatic heterocyclic group, each of which may besubstituted, and Z represents a carbamoyl group.
 2. The color-developingagent as claimed in claim 1, wherein Z in the formula (1) is a carbamoylgroup, which is a carbamoyl group having one or more hydrogen atomsbonded on the nitrogen atom of the carbamoyl group.
 3. Acolor-developing agent represented by the following formula (2):

wherein X¹ represents a halogen atom, an alkylthio group, analkylsulfonyl group, an arylthio group, an arylsulfonyl group or asulfamoyl group, provided that a further substituent which can besubstituted on X¹ excludes a hydroxy group, a carboxyl group, a mercaptogroup, an aminosulfonyl group, a carbonylaminosulfonyl group, asulfonylamino group and a sulfonylaminocarbonyl group, Z¹ represents acarbamoyl group.
 4. The color-developing agent as claimed in claim 3,wherein Z¹ in the formula (2) is a carbamoyl group, which is a carbamoylgroup having one or more hydrogen atoms bonded on the nitrogen atom ofthe carbamoyl group.